GAS  AND  FUEL  ANALYSIS 
FOR  ENGINEERS. 


A  COMPEND  FOR  THOSE  INTERESTED  IN  THE 
ECONOMICAL  APPLICATION  OF  FUEL 


PREPARED  ESPECIALLY  FOR  THE  USE  OF  STUDENTS 

at  the 
MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY. 


BY 

AUGUSTUS  H.   GILL,  S.B.,  PH.D., 

Professor  of  Technical  Analysis  at  the 

Massachusetts  Institute  of  Technology,  Cambridge,  Mass. 

Author  of  "A  Short  Handbook  of  Oil  Analysis, ' ' 

' '  Engine  Room  Chemistry. ' ' 


'    '    •  ' 

EIGHTH  REVISED  EDITION. 
TOTAL  ISSUE,   EIGHT   THOUSAND. 

NEW  YORK 

JOHN  WILEY  &  SONS,  INC. 

LONDON:  CHAPMAN  &  HALL,  LIMITED 

1917 


o 


COPYRIGHT,  1896,  1902,  1907,  1908,  1911,  1913,  1917, 

BY 
AUGUSTUS  H.   GILL. 


PRESS  OF 

BRAUNWORTH  &  CO. 

BOOK  MANUFACTURERS 

BROOKLYN,   N.  Y. 


PREFACE. 


THIS  little  book  is  an  attempt  to  present  in  a  con- 
cise yet  clear  form  the  methods  of  gas  and  fuel  analy- 
sis involved  in  testing  the  efficiency  of  a  boiler  plant. 
Its  substance  was  given  originally,  in  the  form  of 
lectures  and  heliotyped  notes,  to  the  students  in  the 
courses  of  Chemical,  Mechanical,  and  Electrical  En- 
gineering, but  in  response  to  requests  it  has  been 
deemed  expedient  to  give  it  a  wider  circulation. 

At  the  time  of  its  conception,  nothing  of  the  kind 
was  known  to  exist  in  the  English  language;  in 
German  we  now  have  the  excellent  little  book  of  Dr. 
Ferdinand  Fischer,  "  Taschenbuch  fur  Feuerungs- 
Techniker." 

The  present  book  is  the  result  of  six  years'  experi- 
ence in  the  instruction  of  classes  of  about  one  hun- 
dred students.  It  is  in  no  sense  a  copy  of  any  other 
work,  nor  is  it  a  mere  compilation.  The  author  has 
in  every  case  endeavored  to  give  credit  where  any- 
thing has  been  taken  from  outside  sources;  it  is,  how- 

3G7513  m 


IV  PREFACE. 

ever,  difficult  to    credit    single  ideas,  and    if   he   has 
been  remiss  in  this  respect  it  has  been  unintentional. 

The  study  of  flue-gas  analysis  enables  the  engineer 
to  investigate  the  various  sources  of  loss ;  and  if  this 
compend  stimulates  and  renders  easy  such  investiga- 
tion, the  writer's  purpose  will  have  been  accomplished. 
The  necessary  apparatus  can  be  obtained  from  the 
leading  dealers  in  New  York  City. 

The  author  wishes  to  acknowledge  his  indebtedness 
to  our  former  Professor  of  Analytical  Chemistry,  Dr. 
Thomas  M.  Drown,  and  to  Mrs.  Ellen  H.  Richards, 
by  whose  efforts  the  department  of  Gas  Analysis  was 
established. 

He -will  also    be  grateful  for  any  suggestions  or  cor 
rections  from  the  profession. 

MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY, 
BOSTON,  November,  1896. 


PREFACE  TO  THE  EIGHTH  EDITION. 

THE  changes  made  in  the  present  edition  have 
taken  place  mainly  in  the  directions  for  the  bomb 
calorimeter,  which  have  been  made  to  agree  more 
closely  with  present  usage. 

As  in  the  past,  minor  additions  and  corrections  have 
been  made  where  necessary  to  bring  the  book  up  to 
present  practice. 

MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY, 
Cambridge,  December, 


CONTENTS. 


CHAPTER  L 

MM 

INTRODUCTION.      SAMPLING  —  Sampling-tubes.      SUCTION  APPA- 
RATUS.   GAS-HOLDERS i 


CHAPTER  II. 

APPARATUS  FOR  THE  ANALYSIS  OF  CHIMNEY-GASES.    Apparatus  of 

Orsat,  Bunte,  and  Elliott " 

CHAPTER  III. 

THE     MEASUREMENT     OF     TEMPERATURE.    Thermometers — Le 

Chatelier  Pyrometer — Metals  and  Salts 33 

CHAPTER  IV. 

CALCULATIONS.  "Pounds  of  Air  per  Pound  of  Coal,"  and  Per- 
centage of  Heat  Carried  off  by  the  Flue-gases.  Loss  due  to 
Formation  of  Carbonic  Oxide.  Loss  due  to  Unconsumed 
Fuel «8 

CHAPTER  V. 

APPARATUS  FOR  THE  ANALYSIS  OF  FUEL  AND  ILLUMINATING  GASES. 

Apparatus  of  Hempel 36 

CHAPTER  VI. 

PREPARATION  OF  REAGENTS  AND  ARRANGEMENT  or  THE  LABORA- 
TORY    5* 

v 


VI  CONTENTS. 

CHAPTER  VII. 

PAGE 

FUELS,  SOLID,  LIQUID,  AND  GASEOUS  :  THEIR  DERIVATION  AND 
COMPOSITION 58 

CHAPTER  VIII. 

FUELS.  METHODS  OF  ANALYSIS  AND  DETERMINATION  OF  THE 
HEATING  VALUE.  Determination  of  the  Various  Constituents. 
The  Emerson  Bomb  and  Junkers'  Gas-calorimeter 72 

APPENDIX. 

TABLES 113 

COAL  AND  FUEL  OIL  SPECIFICATIONS * n 


LIST  OF   ILLUSTRATIONS. 


1.  GAS  SAMPLING-TUBE '. 3 

2.  SAMPLING  APPARATUS 4 

3.  SAMPLING  APPARATUS  FOR  MINE-GASES 5 

4.  GAS-TUBE 5 

5.  RICHARDS'S  JET-PUMP 8 

6.  BUNSEN'S  PUMP 8 

7.  STEAM  AIR-PUMP 9 

8.  ORSAT  GAS  APPARATUS xa 

9.  BUNTE  GAS  APPARATUS 17 

10.  ELLIOTT  GAS  APPARATUS 21 

11.  MELTING-POINT  BOXES 27 

1 2.  HEMPEL  GAS  APPARATUS 37 

13.  HEMPEL  GAS  APPARATUS 38 

14.  MUENCKE'S  ASPIRATOR 56 

15.  COMBUSTION-FURNACE 74 

16.  EMERSON  BOMB 83 

1 7.  EMERSON  BOMB  AND  CALORIMETER 84 

18.  MAUJER'S  CHART 101 

19.  JUNKERS'  GAS-CALORIMETER,  SECTION 103 

20.  JUNKERS'  GAS-CALORIMETER 104 

ffl 


GAS  AND   FUEL  ANALYSIS. 


CHAPTER    I. 
INTRODUCTION   AND   METHODS    OF   SAMPLING. 

UNTIL  within  recent  years,  the  mechanical  engineer 
in  testing  a  boiler  plant  has  been  compelled  to  con- 
tent himself  with  the  bare  statement  of  its  efficiency, 
little  or  no  idea  being  obtained  as  to  the  apportion- 
ment of  the  losses.  Knowing  the  composition  and 
temperature  of  the  chimney-gases  and  the  analysis  of 
the  coal  and  ash,  the  loss  due  to  the  formation  of  car- 
bonic oxide,  to  the  imperfect  combustion  of  the  coal, 
to  the  high  temperature  of  the  escaping  gases,  can 
each  be  determined  and  thus  a  basis  for  their  reduc- 
tion to  a  minimum  established. 

By  the  simple  analysis  of  the  chimney-gases  and 
determination  of  their  temperature,  a  very  good  idea 
of  the  efficiency  of  the  plant  can  be  obtained  previous 
to  making  the  engineering  test.  For  example,  in  a 
test  which  the  author  made  in  connection  with  his 
students,  the  efficiency  was  increased  from  58  to  70 
per  cent,  upon  the  results  of  the  gas  analysis  alone. 


2  GAS   AND    FUEL   ANALYSIS. 

To  this  end  a  representative  sample  must  be  collected 
according  to  the  method  about  to  be  described. 
SAMPLING.* 

Before  proceeding  to  take  a  sample  of  the  gas,  the 
plant — for  example,  a  boiler  setting — from  which  the 
gas  is  to  be  taken  should  be  thoroughly  inspected, 
and  all  apertures  by  which  the  air  can  enter,  carefully 
stopped  up.  A  suitable  tube  is  then  inserted  air-tight 
in  the  gas-duct,  connected  with  the  sampling  or  gas 
apparatus,  and  suction  applied,  thus  drawing  the  gas 
out.  Cork,  putty,  plaster  of  Paris,  wet  cotton-waste, 
or  asbestos  may  be  used  to  render  the  joint  gas-tight. 
The  place  of  insertion  should  be  chosen  where  the  gas 
will  be  most  completely  mixed  and  least  contaminated 
with  air.  The  oil-bath  containing  the  thermometer  is 
similarly  inserted  near  the  gas-tube,  and  the  tempera- 
ture read  from  time  to  time. 

I.  Tubes. — The  tubes  usually  employed  are  'Bohe- 
mian-glass combustion  tubing  or  water-cooled  metal 
tubes;  those  of  porcelain  or  platinum  are  also  some- 
times used.  Glass  and  porcelain  tubes  when  subjected 
to  high  temperatures  must  be  previously  warmed  or 
gradually  inserted:  the  former  may  be  used  up  to 
temperatures  of  600°  C.  (1200°  F.).  Uncooled  metal 
tubes,  other  than  those  of  platinum,  should  under  no 
circumstances  be  used.f 

*  See  Bureau  Mines  Bulletin  97,  "  Sampling  and  Analyzing  Flue 
Gases,"  1915. 

f  Fischer,  "  Technologie  der  Brennstoffe,"  1880,  p.  221,  states  that 
the  composition  •  of  a  gaseous  mixture  was  changed  from  1.5  to  26.0 
per  cent  carbon  dioxide,  by  the  passage  through  an  iron  tube  heated  to  a 
dull  red  heat,  the  carbonic  oxide  originally  present  reducing  the  iron 
oxide  with  the  formation  of  carbon  dioxide;  this  can  take  place  at  250°. 
(Campbell  "  Manufacture  of  Iron  and  Steel,  p.  53,") 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      3 

The  metal  tube  with  the  water  cooling  is  made  as 
shown  in  Fig.  I,  c  being  a  piece  of  brass  pipe  3 
feet  long,  \\  inches  outside  diameter,  b  the  same 
length,  J  mch  in  diameter,  and  a  \  inch  in  diameter. 
The  water  enters  at  d  and  leaves  at  e.  The  walls  of 


FIG.  i.— GAS-SAMPLING  TUBE. 

the  tubes  are  TV  inch  thick.  The  joint  at  A  should 
be  brazed;  the  others  may  be  soldered. 

Quartz  tubes  can  be  used  in  place  of  the  water-cooled 
metal  tubes  and  have  the  advantage  that  they  require  no 
previous  warming. 

2.  Apparatus  for  the  Collection  of  Samples. — 
A  convenient  sampling  apparatus  is  shown  in  Fig.  2. 
It  may  be  made  from  a  liter  separatory  funnel — in- 
stead of  the  bulb  there  shown — fitted  with  a  rubber 
stopper  carrying  a  tube  passing  to  the  bottom  and  a 
T  tube;  both  of  these,  except  where  sulphur-con- 
taining gases  are  present,  can  advantageously  be 
made  of  T\-inch  lead  pipe.  The  stopper  should  not 
be  fastened  down  with  wire  between  the  tubes  after 
the  manner  of  wiring  effervescent  drinks,  as  this 
draws  the  rubber  away  from  the  tubes  and  occasions 
a  leak.  The  fastening  shown  consists  of  a  brass  .plate 
fitting  upon  the  top  of  the  stopper,  provided  with 
screws  and  nuts  which  pass  through  a  wire  around 


4  GAS  AND   FUEL   ANALYSIS. 

the  neck  of  the  separatory.      A  chain  fastened  to  the 
plate  serves  as  a  convenient  method  of  handling  it. 

In  using  the  apparatus,  the  bulb  is  filled  with  water 
by  connecting  the  stem  with  the  water-supply  and 
opening  one  of  the  pinchcocks  upon  the  T  tube;  the 


FIG.  2.— SAMPLING  APPARATUS. 

water  thus  entering  from  the  bottom  forces  the  air 
out  before  it.  One  branch  of  the  T  is  connected  with 
the  sampling-tube  and  the  other  with  the  suction- 
pump,  the  stopcocks  being  open,  and  a  current  of  gas 
drawn  down  into  the  pump;  upon  opening  the  cock 
upon  the  stem,  the  water  runs  out,  drawing  a  small 
portion  of  the  gas-current  passing  through  the  T  after 
it  into  the  bulb.  It  is  then  taken  to  a  convenient 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      5 

place  for  analysis,  the  tube  //  connected  with  a  head  of 
water,  a  branch  of  the  T  i,  with  the  gas  apparatus,  and 
a  sample  of  gas  forced  over  into  the  letter  for  analysis. 


FIG.  4. — GAS-TUBE.      FIG.  3. — SAMPLING  APPARATUS  FOR 

MINE  GASES. 

Enough  water  should  be  left  in  the  bulb  to  seal  the 
stopcock  on  the  bottom  and  prevent  leakage.  This 
apparatus  is  better  adapted  for  the  needs  of  the  class- 


O  GAS  AND   FUEL   ANALYSIS. 

room  than  for  actual  practice,  as  it  enables  the  same 
sample  to  be  given  to  eight  or  ten  students.  As  has 
been  shown  by  several  years'  experience,  the  water 
exercises  no  appreciable  solvent  action  upon  the 
gaseous  mixture  in  the  time — about  half  an  hour — 
necessary  to  collect  and  distribute  the  samples.  It  is 
often  necessary  to  attach  about  a  yard  of  £-inch 
rubber  tubing  to  the  stem  of  the  bulb  to  prevent  air 
being  sucked  up  through  it  when  taking  a  sample. 

In  the  actual  boiler-test  it  is  preferable  to  insert  a  T 
instead  of  this  apparatus  in  the  gas-stream,  connect  the 
gas  apparatus  to  the  free  branch  of  this  T,  and  draw  the 
sample.  In  making  connections  with  gas  apparatus 
the  air  in  the  rubber  connectors  should  be  displaced 
with  water  by  means  of  a  medicine-dropper. 

In  the  Saxon  coal-mines,  zinc  cans  *  of  ten  liters 
capacity,  of  the  form  shown  in  Fig.  3,  are  used  by  Wink- 
ler  for  sampling  the  mine-gases;  they  are  carried  down 
filled  with  water  and  this  allowed  to  run  out,  and  the 
gas  thus  obtained  brought  into  the  laboratory  and  anal- 
yzed. Small  samples  of  gas  may  very  well  be  taken 
in  tubes  of  100  cc.  capacity  like  Fig.  4,  the  ends  of  which 
are  closed  with  rubber  connectors  and  glass  plugs.  Rub- 
ber bags  are  not  to  be  recommended  for  the  collection 
and  storage  of  gas  for  analysis,  as  they  permit  of  the 
diffusion  of  gases,  notably  hydrogen. 

3.  Apparatus  for  Producing  Suction. — I.  WATER- 
PUMPS — (a)  Jet-pumps,  depending  for  their  action 
upon  a  considerable  head  of  water,  and  (b)  those  depending 
rather  upon  a  sufficient  fall  of  water. 

*  If  used  with  gases  containing  CO2,  it  attacks  the  zinc.  Murmann, 
Oes.  Ch.  Ztg.,  17,  69  (1914). 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      7 

(a)  Jet -pumps. — The  Richards'  jet  pump*  is  shown 
in    section    in    Fig.    5    and   much    resembles   a   boiler 
injector;  it  consists  of  a  water-jet  w,  a  constriction  or 
waist  a,  a  waste-tube  o,  and  a  tube  for  the  inspiration 
of   air.     The   jet   of   water   forms   successive    pistons 
across  a,  drawing  the  air  in  with  it  and  is  broken  up 
into  foam  by  the  zigzag  tube  o. 

This  pump  is  known  in  Germany  as  Muencke's,  and 
in  England  as  Wing's;  Chapman's  pump  is  also  a 
modified  form. 

-It  may  be  easily  constructed  in  glass,  the  jets  pass- 
ing through  rubber  stoppers  which  are  wired  down, 
thus  admitting  of  adjustment  to  the  conditions  under 
which  it  has  to  work.f 

(b)  Fall-pumps. — Bunsen's  pump,   Fig.  6,   consists 
of  a  wide  glass  tube  A,  drawn  out  at  the  bottom  for 
connection  with  a  £-inch  lead   pipe  ^,  and  at  the  top 
for  connection  with  c,  the  tube  through  which  the  air 
is  drawn;  this  tube  is  usually  fused  in,   although   it 
may  be 'connected   with  rubber;  a  is  a  rubber  tube 
provided  with  screw  cocks  connected  with  the  water- 
supply;  d  is  connected  with  a  mercury  column,  and 
the  vessel  B  serves  for  the  retention   of  any  water 
which  might  be  drawn  back  into  the  apparatus  evac- 
uated. 

The  tube  b  for  the  best  result?  should  be  32  feet  in 
length,  equal  to  the  height  of  a  column  of  water  sup- 
ported by  the  atmosphere,  although  for  the  ordinary 
purposes  of  gas-sampling  it  may  be  shorter. 

When  water  is  admitted  through  a  it  fills  b,  acting 

*  Richards,  Am.  Jour,  of  Science  (3),  8,  412;  Trans.  Am.  Inst. 
Min.  Engrs.,  6,  492  (1874). 

f  The  pump  *vill  also  work  well  using  steam. 


8 


GAS  A#D   FUEL   ANALYSIS. 


as  a  continually  falling  piston  drawing  the  current  of 
air  through  e  and  its  connections.  These  various 
forms  of  water-pumps  should  give  a  vacuum  repre- 


FOAM 


JTIG>  5. — RICHARDS'  JET-PUMP.       FIG.  6. — BUNSEN'S  PUMP. 

sented  by  the  height  of  the  barometer  less  the  tension 
of  aqueous  vapor  at  the  temperature  at  which  they 
are  used,  or  about  29  inches  of  mercury. 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      9 

II.  STEAM-PUMPS. — Kochinke  describes  the  appa- 
ratus in  use  in  the  Muldner  Hutten  in  Freiberg, 
shown  at  one-fifth  size  in  Fig.  7.  It  consists  of  a 
glass  tube  drawn  down  to  an  opening  6  mm.  in  diam- 


FIG.  7. — STEAM  AIR-PUMP. 

eter;  concentric  with  this,  and  held  in  place  by  the 
washer  a,  is  the  steam-jet  2  mm.  in  diameter,  passing 
through  the  cork  b,  the  cement  c,  and  covering  d.  It 
is  connected  with  the  steam-pipe  at  g  by  webbed 
rubber  tubing/;  the  air  enters  at  e.  This  is  said  to 
give  very  good  results  and  be  economical  in  use  of 
steam. 

In  case  neither  water  nor  steam  be  available, 
recourse  must  be  had  to  the  ordinary  rubber  syringe- 
bulbs,  provided  with  suitable  valves,  obtainable  at  any 
rubber  store,  or  to  a  bottle  aspirator.  This  consists  of 
two  one-gallon  bottles,  provided  with  doubly  perfor- 
ated rubber  stoppers,  carrying  tubes  of  glass  or  lead 
bent  at  right  angles.  In  each  bottle  one  of  these  tubes 
passes  nearly  to  the  bottom,  and  these  are  connected 
together  by  a  piece  of  rubber  tubing  a  yard  long, 
carrying  a  screw  pinchcock.  The  other  tube  in  each 
case  stops  immediately  under  the  stopper.  Upon 
filling  one  of  the  bottles  with  water,  inserting  the 
stopper  and  blowing  strongly  through  the  shcrt  tube, 
water  will  fill  the  long  tubes  thus  forming  a  siphon, 


IO  GAS  AND   FUEL  ANALYSIS. 

and  upon  lowering  the  empty  bottle,  a  current  of  air 
will  be  sucked  in  through  the  short  tube  originally 
blown  into ;  this  may  be  regulated  by  the  screw 
pinchcock. 

In  inserting  the  gas-sampling  tube  care  should  be 
taken  not  to  insert  it  so  close  to  the  source  of  heat 
as  to  draw  out  the  gases  in  a  dissociated,  i.e.  partly 
decomposed,  condition. 

In  case  of  very  smoky  fuels  it  is  well  to  filter  the 
gases  through  rolls  of  fine  wire  gauze  or  asbestos; 
in  sucking  them  through  a  washing-bottle,  the  water 
may  change  the  composition  of  the  sample. 


CHAPTER   II. 

APPARATUS    FOR    THE   ANALYSIS  OF    CHIMNEY- 
GASES. 

IN  the  writer's  opinion  the  apparatus  which  is  best 
adapted  for  this  purpose  is  that  of  Orsat;  it  is  readily 
portable,  not  liable  to  be  broken,  easy  to  manipulate, 
sufficiently  accurate,  and — in  the  modification  about  to 
be  described — always  ready  for  use,  there  being  no 
stopcocks  to  stick  fast. 

As  the  Bunte  and  Elliott  apparatus  are  also  used 
for  this  purpose,  they  too  will  be  described. 

Fischer's  apparatus,  using  mercury,  is  rather  too 
difficult  for  the  average  engineer;  HempePs  or  More- 
head's*  apparatus  for  the  analysis  of  illuminating-gas 
might  also  be  used;  it  is,  however,  not  customary. 

ORSAT   APPARATUS. 

Description. — The  apparatus  Fig.  8,  is  enclosed  in 
a  case  to  permit  of  transportation  from  place  to  place; 
furthermore,  the  measuring-tube  is  jacketed  with 
water  to  prevent  changes  of  temperature  affecting  the 
gas-volume.  The  apparatus  consists  essentially  of 
the  levelling-bottle  A,  the  burette  B,  the  pipettes 
Pf,  P",  P'"<  and  the  connecting  tube  T. 

*  No.  143  Lake  Street,  Chicago. 

XI 


12  GAS  AND   FUEL  ANALYSIS. 

Manipulation. — The  reagents  in  the  pipettes  should 
be  adjusted  in  the  capillary  tubes  to  a  point  on  the 
stem  about  midway  between  the  top  of  the  pipette 
and  the  rubber  connector.  This  is  effected  by  open- 
ing wide  the  pinchcock  upon  the  connector;  the 


FIG.  8.  — ORSAT'S  GAS  APPARATUS. 

bottle  being  on  the  table,  and  very  gradually  lower- 
ing the  bottle  until  the  reagent  is  brought  to  the  point 
above  indicated.  Six  inches  of  the  tubing  used  corre- 
spond to  but  O.I  cc.,  so  that  an  error  of  half  an  inch 
in  adjustment  of  the  reagent  is  without  influence 
upon  the  accuracy  of  the  result.  The  reagents  having 
been  thus  adjusted,  the  burette  and  connecting  tube 
are  completely  filled  with  water  by  opening  d  and 
raising  the  levelling-bottle.  The  apparatus  is  now 


ANALYSIS  OF  CHIMNEY-GASES.  1 3 

ready  to  receive  a  sample  of  gas  (or  air  for  prac- 
tice). In  case  a  flue-gas  is  to  be  analyzed  d  is  con- 
nected with  z,  Fig.  2,  A  lowered  and  about  102  cc. 
of  the  gas  forced  over  by  opening  //;  or  d  may 
be  connected  with  aT  joint  in  the  gas-stream;  the 
burette  after  filling  is  allowed  to  drain  one  minute  by 
the  sand-glass,  c  snapped  upon  its  rubber  tube,  and 
the  bottle  A  raised  to  the  top  of  the  apparatus.  By 
gradually  opening  c  the  water  is  allowed  to  run  into 
the  burette  until  the  lower  meniscus  stands  upon  the 
100  or  o  mark  (according  to  the  graduation  of  the 
apparatus).  The  gas  taken  is  thus  compressed  into 
the  space  occupied  by  100  cc.,  and  by  opening  d  the 
excess  escapes.  Open  c  and  bring  the  level  of  the 
water  in  the  bottle  to  the  same  level  as  the  water  in  the 
burette  and  take  the  reading,  which  should  be  100  cc. 
Special  attention  is  called  to  this  method  of  reading: 
if  the  bottle  be  raised,  the  gas  is  compressed;  if 
lowered,  it  is  expanded. 

Determination  of  Carbon  Dioxide. — The  gas  to  be 
analyzed  is  invariably  passed  first  into  pipette  P* ',  con- 
taining potassium  hydrate  for  the  absorption  of  carbon 
dioxide,  by  opening  e  and  raising  A.  The  gas  dis- 
places the  reagent  in  the  front  part  of  the  pipette, 
laying  bare  the  tubes  contained  in  it,  which  being 
covered  with  the  reagent  present  a  large  absorptive 
surface  to  the  gas;  the  reagent  moves  into  the  rear 
arm  of  the  pipette,  displacing  the  air  over  it  into  the 
flexible  rubber  bag  which  prevents  its  diffusion  into 
the  air.  The  gas  is  forced  in  and  out  of  the  pipette 
by  raising  and  lowering^,  the  reagent  finally  brought 
approximately  to  its  initial  point  on  the  stem  of  the 


14  GAS  AND   FUEL   ANALYSIS. 

pipette,  the  burette  allowed  to  drain  one  minute,  and 
the  reading  taken.  The  difference  between  this  and 
the  initial  reading  represents  the  cubic  centimeters  of 
carbon  dioxide  present  in  the  gas.  To  be  certain  that 
all  the  carbon  dioxide  is  removed,  the  gas  should  be 
passed  a  second  time  into  P'  and  the  reading  taken 
as  before;  these  readings  should  agree  within  o.  I  per 
cent.  \ 

Determination  of  Oxygen. — The  residue  from  the 
absorption  of  carbon  dioxide  is  passed  into  the  second 
pipette,  P",  containing  an  alkaline  solution  of  potas- 
sium pyrogallate,  until  no  further  absorption  will  take 
place.  The  difference  between  the  reading  obtained 
and  that  after  the  absorption  of  carbon  dioxide,  repre- 
sents the  number  of  cubic  centimeters  of  oxygen 
present. 

Determination  of  Carbonic  Oxide. — The  residue 
from  the  absorption  of  oxygen  is  passed  into  the  third 
pipette,  P'",  containing  cuprous  chloride,  until  no 
further  absorption  takes  place;  that  is,  in  this  case 
until  readings  agreeing  exactly  (not  merely  to  o.  i)  are 
obtained.  The  difference  between  the  reading  thus 
obtained  and  that  after  the  absorption  of  oxygen, 
represents  the  number  of  cubic  centimeters  of  carbonic 
oxide  present. 

Determination  of  Hydrocarbons.  —  The  residue 
left  after  all  absorptions  have  been  made  may  consist, 
in  addition  to  nitrogen,  the  principal  constituent,  of 
hydrocarbons  and  hydrogen.  Their  determination  is 
difficult  for  the  inexperienced,  and,  if  desired,  a  sample 
of  the  flue-gas  should  be  taken,  leaving  as  little  water 


ANALYSIS  OF  CHIMNEY-GASES.  1 5 

in  the  apparatus  as  possible,  and  sent  to  a  competent 
chemist  for  analysis. 

Accuracy. — The  apparatus  gives  results  accurate  to 
0.2  of  one  per  cent. 

Time  Required. — About  twenty  minutes  are  re- 
quired for  an  analysis;  two  may  be  made  in  twenty-five 
minutes,  using  two  apparatus. 

Notes. — The  method  of  adjusting  the  reagents  is  the 
only  one  which  has  been  found  satisfactory:  if  the 
bottle  be  placed  at  a  lower  level  and  an  attempt  made 
to  shut  the  pinchcock  c  upon  the  connector  at  the 
proper  time,  it  will  almost  invariably  result  in  failure. 

The  process  of  obtaining  100  cc.  of  gas  is  exactly 
analagous  to  filling  a  measure  heaping  full  of  grain  and 
striking  off  the  excess  with  a  straight-edge ;  it  saves 
arithmetical  work,  as  cubic  centimeters  read  off  repre- 
sent percent  directly. 

It  often  happens  when  e  is  opened,  c  being  closed, 
that  the  reagent  in  P'  drops,  due  not  to  a  leak  as  is 
usually  supposed,  but  to  the  weight  of  the  column  of 
the  reagent  expanding  the  gas. 

The  object  of  the  rubber  bags  is  to  prevent  the 
access  of  air  to  the  reagents,  those  in  P"  and  P'" 
absorbing  oxygen  with  great  avidity,  and  hence  if 
freely  exposed  to  the  air  would  soon  become  useless. 

Carbon  dioxide  is  always  the  first  gas  to  be  removed 
from  a  gaseous  mixture.  In  the  case  of  air  the  per- 
centage present  is  so  small,  0.08  to  o.  I,  as  scarcely  to 
be  seen  with  this  apparatus.  It  is  important  to  use 
the  reagents  in  the  order  given ;  if  by  mistake  the  gas 
be  passed  into  the  second  pipette,  it  will  absorb  not 
only  oxygen,  for  which  it  is  intended,  but  also  carbon 


1 6  GAS  AND   FUEL   ANALYSIS. 

dioxide;  similarly  if  the  gas  be  passed  into  the  third 
pipette,  it  will  absorb  not  only  carbonic  oxide,  but 
also  oxygen  as  well. 

The  use  of  pinchcocks  and  rubber  tubes,  original 
with  the  author,  although  recommended  by  Naef,*  is 
considered  by  Fischer, f  to  be  inaccurate.  The  ex- 
perience of  the  author,  however,  does  not  support 
this  assertion,  as  they  have  been  found  to  be  fully 
as  accurate  as  glass  stopcocks,  and  very  much  less 
troublesome  and  expensive. 

In  case  any  potassium  hydrate  or  pyrogallate  be 
sucked  over  into  the  tube  T or  water  in  A,  the  analysis 
is  not  spoiled,  but  may  be  proceeded  with  by  connect- 
ing on  water  at  d,  opening  this  cock,  and  allowing  the 
water  to  wash  the  tubes  out  thoroughly.  The  addi- 
tion of  a  little  hydrochloric  acid  to  the  water  in  the 
bottle  A  will  neutralize  the  hydrate  or  pyrogallate,  and 
the  washing  may  be  postponed  until  convenient. 

After  each  analysis  the  number  of  cubic  centimeters 
of  oxygen  and  carbonic  oxide  should  be  set  down  upon 
the  ground-glass  slip  provided  for  the  purpose.  By 
adding  these  numbers  and  subtracting  their  sum  from 
the  absorption  capacity  (see  Reagents)  of  each  reagent, 
the  condition  of  the  apparatus  is  known  at  any  time, 
and  the  reagent  can  be  renewed  in  season  to  prevent 
incorrect  analyses. 

BUNTE   APPARATUS. 

Description. — The  apparatus  Fig.  9  consists  of  a 
burette — bulbed  to  avoid  extreme  length — provided 

*  Wagner's  Jahresb.  1885,  p.  423. 

f  Technologic  d.  Brennstoffe,  foot  note  p.  295. 


ANALYSIS   OF  CHIMNEY-GASES. 


at  the  top  with  a  funnel  F  and  three-way  cock/,  and 
a  cock  /  at  the  bottom.  These  stopcocks  are  best 
of  the  Greiner  and  Friedrichs  obliquely  bored  form. 
The  burette  is  supported  upon  a  retort- 
stand  with  a  spring  clamp. 

A  "suction-bottle  "  5,  an  8-oz.  wide- 
mouthed  bottle,  fitted  similarly  to  a 
wash-bottle,  except  that  the  delivery- 
tube  is  straight  and  is  fitted  with  a 
four-inch  piece  of  £-inch  black  rubber 
tubing,  serves  to  withdraw  the  re- 
agents and  water  when  necessary.  A 
reservoir  to  contain  water  at  the  tem- 
perature of  the  room,  fitted  with  a  long 
rubber  tube,  should  be  provided  for 
washing  out  the  reagents  and  filling 
the  burette. 

Manipulation.  —  Before  using  the 
apparatus,  the  keys  of  the  stopcocks 
should  be  taken  out,  wiped  dry,  to- 
gether with  their  seats,  and  sparingly 
smeared  with  vaseline  or  a  mixture  of 
vaseline  and  tallow  and  replaced.  The  FIG.  9.— BUNTE'S 
completeness  of  the  lubrication  can  be  GAS  AppARATUS- 
judged  by  the  transparency  of  the  joint,  a  thoroughly 
lubricated  joint  showing  no  ground  glass.  The 
burette  is  filled  with  water  by  attaching  the  rubber 
tube  to  the  tip  at  /  and  opening  the  stopcocks  at  the 
top  and  bottom ;  j  is  connected  with  the  source  whence 
the  gas  is  to  be  taken,  turned  to  communicate  with 
the  burette  and  opened,  about  102  cc.  of  gas  allowed 
to  run  in,  and/  and  /  closed. 


1 8  GAS  AND    FUEL   ANALYSIS. 

The  cup  F  is  filled  with  water  to  the  25-00.  mark,  j 
turned  to  establish  communication  between  it  and  the 
burette,  the  burette  allowed  to  drain  one  minute  by 
the  sand-glass,  and  the  reading  taken,  the  cup  being 
refilled  to  the  mark  if  necessary.  The  readings  are 
thus  taken  under  the  same  pressure  each  time,  i.e., 
this  column  of  water  plus  the  height  of  the  barometer; 
and  as  the  latter  is  practically  constant  during  the 
analysis,  no  correction  need  be  applied,  it  being  within 
the  limits  of  error. 

Determination  of  Carbon  Dioxide. — The  "  suc- 
tion-bottle "  is  connected  with  the  tip  of  the  burette, 
/  opened,  and  the  water  carefully  sucked  out  nearly  to 
/.  The  bottle  is  now  disconnected,  the  burette  dis- 
mounted from  its  clamp,  using  the  cup  as  a  handle, 
and  the  25  cc.  of  water  turned  out.  The  tip  is 
immersed  under  potassium  hydrate  contained  in  the 
No.  3  porcelain  dish,  and  the  cock  /  opened,  then 
closed,  and  the  tip  wiped  clean  with  a  piece  of  cloth. 
The  burette  is  now  shaken,  holding  it  by  the  tip  and 
the  cup,  the  thumbs  resting  upon  /  and  /;  more 
reagent  is  introduced,  the  absorption  of  the  gas  caus- 
ing a  diminished  pressure,  and  the  operation  repeated 
until  no  change  takes  place.  The  cup  is  now  filled 
with  water,  j  opened,  and  the  reagent  completely 
washed  out  into  an  ordinary  tumbler  placed  beneath 
the  burette.  Four  times  filling  of  F  should  be  suffi- 
cient for  this  purpose.  The  cup  is  now  filled  to  the 
25~cc.  mark,  j  opened,  and  the  reading  taken  as 
before. 

The  difference  between  this  reading  and  the  initial 
represents  the  number  of  cubic  centimeters  of  carbon 


ANALYSIS   OF  CHIMNEY-GASES.  1$ 

dioxide;  this  divided  by  the  volume  of  the  gas  taken 
gives  the  per  cent  of  this  constituent. 

Determination  of  Oxygen. — The  water  is  again 
sucked  out,  and  potassium  pyrogallate  solution  intro- 
duced, similarly  to  potassium  hydrate;  this  is  dis- 
placed by  water,  and  the  reading  taken  as  before. 
The  difference  between  this  and  the  last  reading  is  the 
volume  of  oxygen  present. 

Determination  of  Carbonic  Oxide. — The  water  is 
removed  for  a  third  time,  and  acid  cuprous  chloride 
solution  introduced  and  the  absorption  made  as  before; 
this  is  washed  out,  first  with  water  containing  a  little 
hydrochloric  acid  to  dissolve  the  white  cuprous  chlo- 
ride which  is  precipitated  by  the  addition  of  water, 
and  finally  with  pure  water,  and  the  reading  taken  as 
before.  The  difference  between  this  and  the  preced- 
ing gives  the  volume  of  carbonic  oxide  present. 

Notes. — Especial  care  should  be  taken  not  to  grasp 
the  burette  by  the  bulb,  as  this  warms  the  gas  and 
renders  the  readings  inaccurate.  The  stopcocks  can 
conveniently  be  kept  in  the  burette  by  elastic  bands 
of  suitable  size.  When  the  apparatus  is  put  away  for 
any  considerable  time,  a  piece  of  paper  should  be 
inserted  between  the  key  and  socket  of  each  stopcock 
to  prevent  the  former  from  sticking  fast.  To  ascer- 
tain when  the  absorption  is  complete,  the  burette  is 
mounted  in  its  clamp  and  allowed  to  drain  until  the 
meniscus  is  stationary,  the  dish  containing  the  reagent 
raised  until  the  tip  is  covered,  /opened,  and  any  change 
in  level  noted.  If  the  meniscus  rises,  the  absorption 
is  incomplete  and  must  be  continued;  if  it  remains 
stationary  or  falls,  the  absorption  may  be  regarded  as 


20  GAS  AND   FUEL   ANALYSIS. 

finished.  In  case  the  grease  from  the  stopcocks 
becomes  troublesome  inside  the  burette,  it  may  be 
removed  by  dissolving  it  in  chloroform  and  washing 
out  with  alcohol  and  then  with  water.  The  object  in 
sucking  the  water  not  quite  down  to  /,  thus  leaving  a 
little  water  in  the  burette,  is  to  discover  if  /  leaks,  the 
air  rushing  in  causes  bubbles. 

The  object  in  washing  out  each  reagent  and  taking 
all  readings  over  water  is  to  obviate  corrections  for 
the  tension  of  aqueous  vapor  over  potassium  hydrate, 
hydrochloric  acid,  or  any  of  the  reagents  which  might 
be  employed.  The  tension  of  aqueous  vapor  over 
seven  per  cent  caustic  soda  is  less  than  over  water. 

Accuracy  and  Time  Required. — The  apparatus  is 
rather  difficult  to  manipulate,  but  fairly  rapid — about 
twenty-five  minutes  being  required  for  an  analysis — 
and  accurate  to  one  tenth  of  one  per  cent. 

ELLIOTT   APPARATUS. 

Description. — The  apparatus  Fig.  10  consists  of  a 
burette  holding  100  cc.  graduated  in  tenths  of  a  cubic 
centimeter  and  bulbed  like  the  Bunte  apparatus — the 
bulb  holding  about  30  cc. ;  it  is  connected  with  a 
levelling-bottle  similar  to  the  Orsat  apparatus.  The 
top  of  the  burette  ends  in  a  capillary  stopcock,  the 
stem  of  which  is  ground  square  to  admit  of  close  con- 
nection with  the  " laboratory  vessel,"  an  ungraduated 
tube  similar  to  the  burette,  except  of  125  cc.  capacity. 
The  top  of  this  tl  vessel  "  is  also  closed  with  a  capil- 
lary stopcock,  carrying  by  a  ground-glass  joint  a 
thistle-tube  F,  for  the  introduction  of  the  reagents. 
The  lower  end  of  this  "  vessel  "  is  closed  by  a  rubber 


ANALYSTS  OF  CHIMNEY-GASES. 


21 


75 


stopper  carrying  a  three-way  cock  0,  and  connected 
with  a  levelling-bottle  D.  The 
burette  and  vessel  are  held  upon  a 
block  of  wood — supported  by  a  ring 
stand — by  fine  copper  wire  tight- 
ened by  violin  keys. 

Manipulation. — The  ground-glass 
joints  are  lubricated  as  in  the  Bunte 
apparatus.  The  levelling-bottles  are 
filled  with  water,  the  stopcocks 
opened,  and  the  bottles  raised  until 
the  water  flows  through  the  stop- 
cocks m  and  n.  m  is  connected 
with  the  source  whence  the  gas  to 
be  analyzed  is  to  be  taken,  n  closed, 
D  lowered  and  rather  more  than  100 
cc.  drawn  in,  and  m  closed.  ;/  is 
opened,  D  raised  and  E  lowered, 
nearly  100  cc.  of  gas  introduced, 
and  n  closed;  by  opening  m  and 
raising  D  the  remainder  of  the  gas 
is  allowed  to  escape,  the  tubes  being 
filled  with  water  and  m  closed,  n  is 
opened  and  the  water  brought  to 
the  reference-mark;  the  burette  is 
allowed  to  drain  one  minute,  the 
level  of  the  water  in  E  is  brought 
to  the  same  level  as  in  the  burette, 
and  the  reading  taken. 

Determination  of  Carbon  Dioxide — By  raising  E, 
opening  n,  and  lowering  D,  the  gas  is  passed  over  into 
the  laboratory  vessel;  F  is  filled  within  half  an  inch 


FIG.  10. — ELLIOTT 
GAS  APPARATUS. 


22  GAS  AND   FUEL  ANALYSIS. 

of  the  top  with  potassium  hydrate,  o  closed,  m  opened, 
and  the  reagent  allowed  to  slowly  trickle  in.  A  No.  3 
evaporating-dish  is  placed  under  <?,  and  this  turned  to 
allow  the  liquid  in  the  laboratory  vessel  to  run  into 
the  dish.  At  first  this  is  mainly  water,  and  may  be 
thrown  away;  later  it  becomes  diluted  reagent  and 
may  be  returned  to  the  thistle-tube.  When  the 
depth  of  the  reagent  in  the  thistle-tube  has  lowered 
to  half  an  inch,  it  should  be  refilled  either  with  fresh 
or  the  diluted  reagent  and  allowed  to  run  in  until  the 
absorption  is  judged  to  be  complete,  and  the  gas 
passed  back  into  the  burette  for  measurement.  To 
this  end  close  o  and  then  m,  raise  E,  open  ;/,  and 
force  some  pure  water  into  the  laboratory  vessel,  thus 
rinsing  out  the  capillary  tube.  Now  raise  D  and  lower 
E,  shutting  n  when  the  liquid  has  arrived  at  the  refer- 
ence-mark. The  burette  is  allowed  to  drain  a  minute, 
the  level  of  the  water  in  the  bottle  E  brought  to  the 
same  level  as  the  water  in  the  burette,  and  the  reading 
taken. 

Determination  of  Oxygen. — The  manipulation  is 
the  same  as  in  the  preceding  determination,  potassium 
pyrogallate  being  substituted  for  potassium  hydrate; 
the  apparatus  requiring  no  washing  out. 

Determination  of  Carbonic  Oxide. — The  labora- 
tory vessel,  thistle-tube,  and  bottle  if  necessary,  are 
washed  free  from  potassium  pyrogallate  and  the 
absorption  made  with  acid  cuprous  chloride  similarly 
to  the  determination  of  carbon  dioxide.  The  white 
precipitate  of  cuprous  chloride  may  be  dissolved  by 
hydrochloric  acid. 


ANALYSIS  OF  CHIMNEY-GASES.  2$ 

Accuracy  and  Time  Required. — The  apparatus  is 
as  accurate  for  absorptions  as  that  of  Orsat;  it  is 
stated  to  be  much  more  rapid — a  claim  which  the  writer 
cannot  substantiate.  It  is  not  as  portable,  is  more 
fragile,  and  more  troublesome  to  manipulate,  and  as 
the  burette  is  not  jacketed  it  is  liable  to  be  affected 
by  changes  of  temperature. 

Notes. — In  case  at  any  time  it  is  desired  to  stop 
the  influx  of  reagent,  o  should  be  closed  first  and 
then  m\  the  reason  being  that  the  absorption  may 
be  so  rapid  as  to  suck  air  in  through  o,  m  being 
closed. 

The  stopcock  should  be  so  adjusted  as  to  cause  the 
reagent  to  spread  itself  as  completely  as  possible  over 
the  sides  of  the  burette. 

By  the  addition  of  an'  explosion-tube  it  is  used  for 
the  analysis  of  illuminating-gas,*  bromine  being  used 
to  absorb  the  "  illuminants."  Winkler  f  states  that  this 
absorption  is  incomplete;  later  work  by  Treadwell  and 
Stokes,  and  also  Korbuly,{  has  shown  that  bromine  water, 
by  a  purely  physical  solution,  does  absorb  the  "  illumi- 
nants "  completely;  Hempel  §  states  that  explosions  of 
hydrocarbons  made  over  water  are  inaccurate,  so  that 
the  apparatus  can  be  depended  upon  to  give  results  upon 
methane  and  hydrogen  only  within  about  two  per  cent. 

*  Mackintosh,  Am.  Chem.  Jour.  9,  294. 

f  Zeit.  f.  Anal.  Chem.  28,  286. 

I  Treadwell's  Quan.  Analysis  (Hall's  translation),  p.  569. 

§  Gasanalytische  Methoden,  p.  102. 


24  GAS  AND  FUEL  ANALYSIS. 

CARBONIC  ACID  INDICATORS. 

These  usually  depend  upon  the  principle  of  collecting 
100  cc.  of  the  gas,  causing  it  to  pass  through  a  suitable 
absorber  and  collecting  the  residue  in  a  bell  which  floats 
to  a  greater  or  less  height  according  to  the  residual  vol- 
ume. The  fluctuations  of  this  bell  are  recorded  after 
the  usual  manner  of  self-registering  barometers  or  ther- 
mometers; the  usual  time  for  this  analysis  and  record  is 
five  minutes.  The  Gas-composimeter  of  Uehling  *  de- 
pends upon  the  laws  governing  the  flow  of  gases  through 
small  apertures. 

They  are  difficult  to  adjust  and  keep  in  adjustment, 
requiring  to  be  checked  frequently  by  the  Orsat  appa- 
ratus, and  are  expensive.  Their  indications  are  within 
about  half  of  one  per  cent  of  those  given  by  the  chemical 
apparatus.  Only  the  presence  of  carbon  dioxide  is  in- 
dicated by  them. 

*  Gill,  Engine  Room  Chemistry,  pp.  96  and  97. 


CHAPTER   III. 
MEASUREMENT  OF   TEMPERATURE. 

IN  the  majority  of  cases,  the  ordinary  mercurial 
thermometer  will  serve  to  determine  the  temperature 
of  the  chimney-gases.  It  should  not  be  inserted  naked 
into  the  flue,  but  be  protected  by  a  bath  of  cylinder, 
or  raw  linseed  oil,  contained  in  a  brass  or  iron  tube. 
These  tubes  may  be  half  an  inch  inside  diameter  and 
two  to  three  feet  in  length.  Temperatures  as  high  as 
625°  C.  have  been  observed  in  chimneys;  this  lasts  of 
course  but  for  a  moment,  but  would  be  sufficient  to 
burst  the  unprotected  thermometer. 

For  the  observation  of  higher  temperatures,  recourse 
must  be  had  to  the  "  high-temperature  thermom- 
eters," filled  with  carbon  dioxide  under  a  pressure  of 
about  one  hundred  pounds,  giving  readings  to  550°  C.* 
These  may  be  obtained  of  the  dealers  in  chemical 
apparatus;  seme  require  no  bath,  being  provided 
with  a  mercury-bath  carefully  contained  in  a  steel 
tube,  and  the  whole  enclosed  in  a  bronze  tube.f 

*  Those  made  by  W.  Apel,  Gottingen,  Germany,  are  about  three 
feet  long,  the  scale  occupying  about  one  foot,  thus  avoiding  the 
necessity  of  withdrawing  the  thermometer  from  the  bath  for 
reading.  H.  J.  Green  of  Brooklyn,  N.  Y.,  makes  similar  ones. 

f  Hohmann  Special  Thermometers,  made  by  Hohmann  and  Maurer 
Co.,  44  High  Street,  Boston,  Mass. 

25 


26  GAS  AND   FUEL   ANALYSIS. 

These  thermometers  should  be  tested  from  time  to 
time  either  by  comparison  with  a  standard  or  by  inser- 
tion in  various  baths  of  a  definite  temperature.  Some 
of  the  substances  used  for  these  baths  are:  water,  boil- 
ing-point 100° ; naphthalene,  Bpt.  218°;  benzophenon, 
Bpt.  306°;  and  sulphur,*  Bpt.  445°.  Care  should  be 
taken  that  the  bulb  of  the  thermometer  does  not  dip 
into  the  melted  substance,  but  only  into  the  vapor, 
and  that  the  stem  exposure  be  as  nearly  as  possible 
that  in  actual  use. 

For  the  measurement  of  temperatures  beyond  the 
range  of  these  thermometers  the  Le  Chatelier  thermo- 
electric pyrometer  may  be  used.  This  consists  of  a 
couple  formed  by  the  junction  of  a  platinum  and 
platinum-  io#  rhodium  wire,  passing  through  fire-clay 
tubes  in  a  porcelain  or  iron  envelope  and  connected 
with  a  galvanometer.  The  hotter  the  junction  is 
heated  the  greater  the  current  and  the  galvanometer 
deflection;  this  latter  is  determined  for  several  points, 
naphthalene,  sulphur,  and  copper,  Mpt.  1083°  C.,  or 
even  platinum,  1753°  C.,  and  a  plot  made  with  gal- 
vanometer-readings as  abscissae  and  temperatures  as 
ordinates.  From  this  the  temperature  corresponding 
to  any  deflection  is  readily  obtained. 

The  exact  description  of  the  instrument  and  details 
of  calibration  are,  however,  beyond  the  scope  of  this 
work,  and  the  student  is  referred  for  these  to  articles 
by  Le  Chatelier,  Societe"  Technique  de  ITndustrie  du 
Gaz,  1890,  abstracted  in  Jour.  Soc.  Chem.  Industry, 

*  In  testing  the  Hohmann  thermometers  in  sulphur-vapor,  the 
bronze  tube  should  be  prevented  from  corrosion  by  the  vapor  by 
a  glass  envelope. 


MEASUREMENT  OF   TEMPERATURE. 


9,  326,  and  Holman,  Proc.  Am.  Academy,  1895,  p. 
234;  later  works  are  those  of  Burgess  and  Le  Chatelier 
and  Boudouard,  "High  Temperature  Measurements" 
(1912),  and  also  C.  L.  Norton,  "Notes  on  Heat  Meas- 
urements" (1902). 

An  error  of  5°  in  the  reading  of  the  thermometer 
affects  the  final  result  by  about  20  calories. 

In  case  neither  of  these  methods  be  available  nor 


300 


880 


840" 


300 


FIG.  ii. — MELTING-POINT  BOXES. 

applicable,  use  may  be  made  of  the  melting-points 
of  certain  metals  or  salts  contained  in  small  cast-iron 
boxes,  Fig.  II.  The  melting-points  of  certain  metals 
and  salts  are  given  in  Table  VII. 


CHAPTER    IV. 
CALCULATIONS. 

As  has  been  already  stated  in  the  Introduction,  the 
object  of  analyzing  the  flue-gases  is  to  ascertain,  first, 
the  completeness  of  the  combustion,  especially  the 
amount  of  air  which  has  been  used  or  the  "  pounds  of 
air  per  pound  of  coal,"  and  second,  the  amount  of 
heat  passing  up  chimney. 

i.  To  Ascertain  the  Number  of  Pounds  of  Air 
per  Pound  of  Coal. — A  furnace-gas  gives  11.5$  CO,, 
7.4$  O,  o.gfo  CO,  and  80.2$  N.  Data:  atomic  weights, 
O  =  16,  C  =  12;  weight  liter  COa  =  1.966  grs.,  of 
O,  1.43  grs.,  of  CO,  1.251  grs.  Find  the  number  of 
grams  of  each  constituent  in  100  liters  of  the  furnace- 
gas,  and  from  this  the  weight  of  carbon  and  weight  of 
oxygen.  11.5  (liters  CO2)  X  1.97  (wt.  liter  CO2)  = 

22.66  grms.  CO2;  now  — (fvf")  °^  this  'ls  oxygen  = 

16.48  grms.,  6.18  grms.  is  carbon.  The  weight  of 
free  oxygen  is  7.4  X  1.43  =  10.58  grms.  The  weight 
of  carbon  and  oxygen  in  the  carbonic  oxide  is  0.9  X 

„„  AT  l6/    O     \. 

1.25  =1.12  grms.  CO.     Now  -^l-^.  us  oxygen  or  0.64 

28  \COy 

grm.,  and  0.48  grm.  is  carbon.  There  are  then  pres- 
ent in  100  liters  of  the  gas  27.70  grms.  oxygen  and 
6.66  grms.  carbon;  corresponding  to  120.0  grms.  air 

28 


CALCULATIONS.  29 

to  6.66  grms.  carbon,  air  being  23. i#  oxygen  by 
weight;  or  18.02  |£™S"  |  air  per  ^m'  j  carbon.  If 

the  coal  be  83$  carbon,  this  figure  must  be  diminished 
accordingly,  giving  in  this  case  14.9$  Ibs.  air  per  Ib. 
of  coal.  Theory  requires  1 1.54  Ibs.  air  per  Ib.  of  car- 
bon, but  in  practice  the  best  results  are  obtained  by 
increasing  this  from  50$  to  100$.* 

2.  To  Ascertain  the  Quantity  of  Heat  Passing 
up  Chimney  — Determine  the  volume  of  gas  generated 
Jrom  one  kilo  of  coal  when  burned  so  as  to  produce 
the  gas  the  analysis  of  which  has  just  been  made 
according  to  the  directions  given.  The  chemical 
analysis  of  the  coal  is  as  follows:  moisture  1.5^, 
sulphur  1.2$,  carbon  83$,  hydrogen  2.5^,  ash  11.4^, 
oxygen  and  nitrogen  (by  difference)  0.4$.  Then 
there  are  in  one  kilo  of  coal  830  grms.  carbon,  of 
this  suppose  but  800  to  be  burned,  the  remaining  30 
grms.  going  into  the  ash;  of  the  800  grms.  618/666 
or  742  grms.  produced  carbon  dioxide,  and  48/666 
or  58  grms.  produced  carbonic  oxide.  From  6.18 
grms.  carbon  were  produced  11.5  liters  carbon  di- 
oxide in  the  problem  in  I ;  hence  742  grms.  would 
furnish  1381  liters.  6. 18  :  742  :  :  1 1.5  :  y.  ^=1381. 
Similarly  58  grms.  carbon  would  furnish  109.0  liters 
carbonic  oxide.  0.48  :  58  ::  0.90  :  z.  ,2=109.0.  The 
volume  of  oxygen  can  be  found  by  the  proportion 
11.5  (#CO,):  7.4  (#O)::  1381  :  x.  x  =  888  liters.  In 
the  same  manner  the  nitrogen  is  found  to  be  9631 
liters.  1 1.5  :  80.2  :  :  1381  :  u.  #=9631.  One  kilo  of 
coal  under  these  conditions  furnishes  1.381  cu.  meters 

*  Scheurer-Kestner,  Jour.  Soc.  Chem.  Industry,  7,  616.  0.75  Ib. 
per  1000  B.t.u.  Nisbet,  Power.  36,  995  (1912). 


3°  GAS    AND    FUEL    ANALYSTS. 

carbon  dioxide,   0.109   c-   m-   carbonic    oxide,   O.888 
c.  m.  oxygen,  and  9.631  c.  m.  nitrogen. 

The  quantity  of  heat  carried  orf  by  each  gas  is  its 
rise  of  temperature  X  its  weight  X  its  specific  heat. 
The  specific  heats  of  the  various  gases  are  shown  in 
the  table  below,  and  for  facility  in  calculation,  a  column 
is  given  obtained  by  multiplying  the  weight  by  the 
specific  heat;  multiplying  the  volumes  obtained  in  the 
previous  calculation  by  the  numbers  in  this  column 
and  by  the  rise  in  temperature  gives  the  number  of 
calories  (C)  that  each  gas  carries  away. 

TABLE    OF   SPECIFIC    HEATS    OF   VARIOUS    GASES.* 

,  _  Wt.  of  Cu.  M.     Sp.  Heat  X 

Name  of  Gas.  Sp.  Heat.  Rg  WtofCu.M.      L°ff' 

Carbon  dioxide  (io°-35o°).  0.234  r-97  0.463  9.6656 

"        monoxide 0.245  1.26  0.308  9.4886 

Oxygen 0.217  1.43  0.311  9.4928 

Nitrogen., 0.244  1-26  0.306  9.4857 

Aqueous  vapor 0.480  0.80  0-387  9-5877 

In  the  test  the  average  temperature  of  the  escaping 
gases  was  275°  C. ;  that  of  the  air  entering  the  grate 
was  25°  C.,  a  rise  of  temperature  of  250°  C.  As 
shown  by  the  wet-and-dry-bulb  thermometer,  the  air 
was  50  per  cent  saturated  with  moisture. 

The  calculation  of  the  heat  carried  away  is  then  for: 

Cu.  M.  C. 

Carbon  dioxide 1.381  X  250  X  0.463  =  160.0 

Carbonic  oxide o.  109  X     "    X  0.308  =       8.4 

Oxygen 0.888  X     "    X  0.311  =    69.1 

Nitrogen 9-631  X     "X  0.306  =  737.0 


Total 12.009  974-5 

*  Fischer,  Tech.  d.  Brennstoffe,  p.  267. 


CA  L  CULATIONS.  3 1 

There  is,  however,  another  gas  passing  up  chimney 
of  which  we  have  taken  no  cognizance,  namely,  water- 
vapor;  this  comes  from  the  moisture  in  the  coal,  from 
the  combustion  of  hydrogen  in  the  coal,  and  from  the 
air  entering  the  grate;  its  volume  is  calculated  as 
follows: 

The  moisture  in  the  coal  as  found  by  chemical 
analysis  was  1.5$  =  0.015  kg.;  the  hydrogen  in  the 
coal  was  2.5$  =  0.025  kg.  The  amount  of  water  this 
forms  when  burned  is  nine  times  its  weight,  0.025  kg. 
X  9  —  0.225  kg.  The  moisture  in  the  air  entering  the 
grate  would  be,  if  completely  saturated,  22.9  grams 
per  cubic  meter,  as  shown  by  Table  I ;  it  was,  how- 
ever, but  50$  saturated.  The  quantity  is  then,  the 
volume  of  air  used  per  kilogram  of  coal  X  moisture 
contained  in  it,  or  12.009  X  22.9  X  0.50  =  o,  137  kg. 
The  weight  of  aqueous  vapor  passing  up  chimney  per 
kilogram  of  coal  is  0.015  +  0.225  +  o.  137  =  0.377 
kg. ;  the  quantity  of  heat  that  this  carries  off  is  0.377 
X  250  X  0.480  =  45.2  C.  The  total  quantity  of  heat 
passing  up  chimney  is  then  1019.7  C.  The  heat  of 
combustion  of  this  coal  as  found  by  Mahler's  calori- 
metric  bomb  was  7220  C. ;  hence  the  percentage  of 
heat  carried  off  is  1020/7220  =  14.  i#. 

The  preceding  calculations  though  correct  are 
tedious,  so  much  so,  as  to  almost  preclude  their  use 
for  an  hourly  observation  of  the  firing.  They  should 
be  employed,  however,  in  making  the  final  calculation 
of  a  boiler-test,  using  the  averages  obtained. 

Shields  *  has  combined  the  operations  in 

*  Power,  30,  ii2i  (1909). 


32  GAS  AND   FUEL   ANALYSIS. 

I.    Pounds  of  Air  per  Pound  of  Coal  (p.  28),  and 
obtains  the  following  formula: 
Pounds  of  air  per  pound  of  coal 

__  Per  cent,  carbon  in  coal 

2°TPer  cent.  CO2  +  per  cent.  CO. 
Similarly,  Per  cent,  heat  lost 

Per  cent,  carbon  in  coal  200  + per  cent.  CO2 

-_ x X 

Heating  value  of  coal      Percent.  CO2  +  percent.CO 
.     rise  in  temperature  in  °C.Xo.2864. 

The  values  found  by  this  equation  are  0.5  per  cent,  low, 
as  no  cognizance  has  been  taken  of  the  water  vapor. 

In  rapid  work  the  following  formula  will  be  found 
more  applicable:  Let  o  and  n  represent  the  percent- 
ages of  oxygen  and  nitrogen  found  in  the  chimney- 
gas;  then  the  ratio  of  the  air  actually  used  to  that 
theoretically  necessary  is  expressed  by  the  formula, 

21 


Applying    it    in  the    case    of    the    flue-gas    given,   it 
becomes 

21  21 

77   ~~I79X  7-4\  =r  ^7  = 
21  "\     80.2 


Multiplying  this  by  11.54,  the  theoretical  number  of 
pounds  of  air  per  pound  of  carbon,  we  obtain  17.69  as 
against  18.02  on  page  28. 

Bunte  *  has  given  a  shorter  method  for  the  deter- 

*  Jour.   f.    Gasbeleuchtung,   43,    637  (1900)  ;  Abstr.    Jour.  Soc. 
"Ch'/n.  Industry,  19,  887. 


TAB] 

BUNTE'S    CHART   SHOWING    HEAT    LOST    IN    CHIM 

TEMPE] 


CO. 
2500  -19 


2376  -18 

2255  -17 

2131  -16 

2004  15 

1877  14 

1753  13 

1623  12 

o   1493    11 

ut 

g   1361    10 

cc 

UJ 
Q. 

5    1229      9 

UJ 

t- 

g   1096     8 

t- 

UJ 

§     962      7 

UJ 

830  6 

694  5 

557  4 

418  3 

281  2 


10 


30 


141—1 


o-o 


X  \ 


X 


V   \ 


X 


X 


X 


\  \ 


X 


\ 


X 


\  X 


\ 


\ 


X 


\  \ 


X 


PER   CENT 
40 


\ 


XX 


\\ 


XX 


X 


\\ 


\\ 


\\ 


XX 


X 


\ 


\\ 


\\ 


X 


X 


\x\ 


100 


90 


70 


PER  C 


LE   X. 

N'EY-GASES    FROM   THE   CARBONIC    ACID    AND    THE 
RATURE. 

EFFICIENCY 


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30 


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To  face  page  33. 


TABLE  XL 


8 


ACTUAL  TEMPERATURES 


CALCULA  TIONS. 


33 


mination  of  the  quantity  of  heat  passing  up  chimney, 
and  one  which  does  not  involve  the  analysis  of  the 
coal. 

For  every  per  cent  of  carbonic  acid  present  43.43  C. 
per  cubic  meter  of  flue-gases  have  been  developed  =  W\ 
C=  specific  heat  of  the  flue-gases  per  cubic  meter; 
then  W/C  represents  the  initial  temperature  (which  is 
never  attained)  the  ratio  of  which  to  the  actual  exit 
temperature  of  the  flue-gases  shows  the  heat  lost.  If 
T=  this  initial  temperature  and  /  the  rise  of  tempera- 
ture of  the  flue-gases,  then  t/T  represents  the  heat 
lost  in  the  chimney-gases. 

The  following  table  gives  the  data  for  the  calculation 
for  both  pure  carbon  and  coal  of  average  value. 


Initial  Temperature,  W/C.    Degrees  C. 

Per  Cent  of 
/"•  r\    ••* 

Specific  Heat 

CUj  in 
Chimney  Gas. 

Chimney  Gas. 

For  Carbon 

For  Coal 

Diff.  for 

=  T. 

=  T. 

0.1*  CO,. 

I 

0.308 

141 

I67 

Tf) 

2 

0.310 

280 

331 

1  LJ 

16 

3 

0.3H 

419 

493 

TA 

4 

0.312 

557 

652 

IO 

T  f 

5 

0.313 

694 

808 

*5 

T  e 

6 

0.314 

830 

961 

AD 

Y  £ 

7 

0.315 

962 

III2 

Lb 

T  - 

8 

o  316 

1096 

I26l 

!5 

y  f 

9 

0.318 

1229 

1407 

J5 

10 

0.319 

1360 

1550 

T4 

T   1 

ii 

O.32O 

1490 

1692 

*4 

12 

O.322 

1620 

1830 

13 

0.323 

1750 

1968 

M 

14 

0.324 

1880 

2IO2 

T3 

M 

15 

0.324 

2005 

2237 

A  j 

T  1 

16 

0.325 

2130 

2366 

13 

Applying  this  to  the  problem   on  page  29  we  find 
the  initial  temperature    T  to  be  1762°  C.,  the  rise  of 


34  GAS  AND    FUEL   ANALYSIS. 

temperature  of  the  gases  was  250°  C.,  the  loss  is 
250/1762  =  14.2$,  against  14.1$  found  by  the  calcu- 
lation page  31. 

Bunte  also  employs  a  partially  graphical  method  for 
the  determination  of  the  loss  of  heat.  In  Table  X 
the  extreme  left-hand  column  represents  the  tempera- 
tures which  should  be  obtained  by  the  combustion  of 
the  average  coal  with  the  formation  of  a  chimney-gas 
containing  the  percentages  of  carbon  dioxide  in  the 
column  next  it.  Applying  this  to  our  case  we  find 
the  theoretical  temperature  for  11.5$  CO2  to  be  1558°; 
dividing  the  rise  of  temperature  actually  observed  — 
250°  —  by  this,  we  obtain  16.05$,  or  2f°  more  than  by 
the  method  of  page  31. 

Almost  the  identical  result  can  be  obtained  from 
Table  XI  directly:  if  the  point  of  intersection  of  the 
diagonal  representing  the  per  cent  of  carbon  dioxide 
with  the  horizontal  line  denoting  the  actual  tem- 
perature, on  the  right,  be  followed  to  the  bottom  of 
the  table  the  per  cent  of  loss  is  ascertained. 

Table  XI  is  the  lower  right-hand  corner  of  Table  X 
enlarged. 

W.  A.  Noyes*  states  that  the  following  formula 
gives  close  results  and  is  also  independent  of  the  com- 
position of  the  coal. 

Percentage  loss  =  (^o.on-|  ---  ^^  —  lo.  00605  )(*'—  0- 


Lunge  f  has  also  given  a  shorter  method  for  the  cal 
culation  of  the  heat  lost. 

*  Am.  Chem.  Journal,  19,  162. 

•j-  Zeit.  f.  angewandte  Chemie,  1889,  240. 


CALCULATIONS.  35 

The  following  table*  shows  roughly  the  excess  of  air 
and  the  per  cent  of  heat  lost  in  the  chimney  gases: 

PER  CENT  OF  CARBONIC  ACID. 

2     3     4     5     6     7     8     9     10    ii    12    13    14    15 

VOLUME   OF  AIR   MORE   THAN   THEORY. 

(Theory  =  i. o). 

9-5  6-3  4-7  3-8  3-2  2.7  2-4  2.1  1.9  1.7  1.6  1.5  1.4  1.3 

PER    CENT     LOSS     OF    HEAT. 
Temp,  of  chimney  gases,  518°  F. 

go   60  45   36  30   26    23    20   18    16    15    14    13    12 

Determination  of  Loss  Due  to  Formation  of  Car- 
bonic Oxide. — On  page  29  we  see  that  58  grams  of 
carbon  burned  to  carbonic  oxide;  for  every  gram  of 
carbon  burned  to  carbonic  oxide  there  is  a  loss  of 
5.66  C.,  in  this  case  a  loss  of  328  C.  The  heating  value 
of  the  coal  is  7220  C.,  hence  the  loss  is  4.5  per  cent. 

Other  Losses.  Kreisinger  and  Ovitz  (Bureau  Mines 
Bulletin  97,  p.  35),  have  admirably  shown  the  other 
sources  of  loss.  This  is  so  important  that  it  is  here  repro- 
duced, Table  XII. 

*  Arndt's  Econometer  Circular. 


CHAPTER  V. 

APPARATUS    FOR   THE    ANALYSIS   OF    FUEL    AND 
ILLUMINATING   GASES. 

HEMPEL'S  APPARATUS. 

Description. — The  apparatus,  Figs.  12  and  13,  is 
very  similar  in  principle  to  that  of  Orsat ;  the  burette 
is  longer,  admitting  of  the  reading  of  small  quantities 
of  gas,  and  the  pipettes  are  separate  and  mounted  in 
brass  clamps  on  iron  stands.  P  shows  a  "  simple  " 
pipette*  provided  with  a  rubber  bag;  this  form,  after 
ten  years  of  use,  can  be  said  to  satisfactorily  take  the 
place  of  the  cumbersome  "  compound  "  pipette. 

The  pipette  for  fuming  sulphuric  acid  f  is  shown  at 
F,  and  differs  from  the  ordinary  in  that  vertical  tubes 
after  the  manner  of  those  in  the  Orsat  pipettes  replace 
the  usual  glass  beads.  This  prevents  the  trapping  of 
any  gas  by  the  filling,  which  was  so  common  with  the 
beads  and  glass  wool.  E  represents  the  large  explo- 
sion pipette,;};  of  about  250  cc.  capacity,  with  walls  half 
an  inch  thick ;  the  explosion  wires  enter  at  the  top  and 
bottom  to  prevent  short-circuiting;  mercury  is  the 
confining  liquid.  The  small  explosion  pipette  holds 

*  Gill,  Am.  Chem.  J.,  14,  231  (1892). 
f  Id.,  J.  Am.  Chem.  Soc.,  18,  67  (1896). 
\  Gill,  J.  Am.  Chem.  Soc.,  17,  771  (1895). 

36 


APPARATUS.  37 

about  1 10  cc.  and  is  of  glass,  the  same  thickness  as 
the  simple  pipettes.  Water  is  here  used  as  the  confin- 
ing liquid,  and  also  usually  in  the  burette. 

An  induction  coil  capable  of  giving  a  half-inch  spark, 


FIG.  12. — SHOWING  HEMPEL  BURETTE  CONNECTED  WITH  THE 
SIMPLE  PIPETTE  ON  THE  STAND- 

with   a  six-cell   "Samson"    battery,    four    "simple" 
pipettes  and  a  mercury  burette,  complete  the  outfit. 

The  burette  should  be  carefully  calibrated  and  the 
corrections  may  very  well  be  etched  upon  it  opposite 
the  lO-cc.  divisions. 


38  GAS   AND   FUEL   ANALYSIS. 

In  working  with  the  apparatus  the  pipettes  are  placed 
upon  the  adjustable  stand  5  and  connection  made  with 
the  doubly  bent  capillary  tube. 

Manipulation. — To  acquire  facility  with  the  use  of 
the  apparatus  before  proceeding  to  the  analysis  of 


FIG.  13. — EXPLOSION  PIPETTE  FOR  MERCURY  AND  SULPHURIC 
ACID  PIPETTE. 


illuminating-gas,  it  is  well  to  make  the  following  deter- 
minations, obtaining  "  check  readings  "  in  every  case: 
I.  Oxygen  in  air,  by  (i)  absorption  with  phosphorus; 

(2)  absorption  with  potassium  (or  sodium)  pyrogallate; 

(3)  by  explosion  with  hydrogen. 


APPARATUS.  39 

I.    DETERMINATION    OF    OXYGEN   IN    AIR. 

(1)  By  Phosphorus. — 100  cc.  of  air  are  measured 
out   as  with  the   Orsat   apparatus,   the    burette   being 
allowed  to  drain  two  minutes.      The  rubber  connectors 
upon  the  burette  and  pipette  are  filled  with  water,  the 
capillary  tube  inserted,  as  far  as  it  will  go,  by  a  twist- 
ing motion,  into  the  connector  upon  the  burette,  thus 
filling   the   capillary  with  water;   the  free  end  of  the 
capillary   is   inserted   into  the   pipette   connector,    the 
latter  pinched  so   as   to  form   a  channel  for  the  water 
contained  in  it  to  escape,  and  the  capillary  twisted  and 
forced  down  to  the  pinch-cock.      There  should  be  as 
little  free  space  as  possible  between  the  capillaries  and 
the  pinch-cock.      Before  using  a  pipette,  its  connector 
(and   rubber   bag)    should   be   carefully   examined   for 
leaks,    especially  in   the  former,  and  if  any  found  the 
faulty  piece  replaced. 

The  pinch-cocks  on  the  burette  and  pipette  are  now 
opened,  the  air  forced  over  into  the  phosphorus,  and 
the  pinch-cock  on  the  pipette  closed ;  action  im- 
mediately ensues,  shown  by  the  white  fumes;  after 
allowing  it  to  stand  for  fifteen  minutes  the  residue  is 
drawn  back  into  the  burette,  the  latter  allowed  to  drain 
and  the  reading  taken.  The  absorption  goes  on  best 
at  20°  C,  not  at  all  at  below.  15°  C.  ;  it  is  very  much 
retarded  by  small  amounts  of  ethene  and  ammonia. 
No  cognizance  need  be  taken  of  the  fog  of  oxides  of 
phosphorus. 

(2)  By  Pyrogallate  of  Potassium. — 100  cc.  of  air 
are  measured  out  as  before,  the  carbon  dioxide  absorbed 
with  potassium  hydrate  and  the  oxygen  with  potassiurr 


40  GAS  AND   FUEL   ANALYSIS. 

pyrogallate,  as  with  the  Orsat  apparatus ;  before  setting 
aside  the  pyrogallate  pipette,  the  number  of  cubic 
centimeters  of  oxygen  absorbed  should  be  noted  upon 
the  slate  s  on  the  stand.  This  must  never  be  omitted 
with  any  pipette  save  possibly  that  for  potassium 
hydrate,  as  failure  to  do  this  may  result  in  the  ruin  of 
an  important  analysis.  The  reason  for  the  omission  in 
this  case  is  found  in  the  large  absorption  capacity — four 
to  five  litres  of  carbon  dioxide — of  the  reagent. 

(3)  By  Explosion  with  Hydrogen. — 43  cc.  of  air 
and  57  cc.  of  hydrogen  are  measured  out,  passed  into 
the  small  explosion  pipette,  the  capillary  of  the  pipette 
filled  with  water,  the  pinch-cocks  and  glass  stop-cock 
all  closed,  a  heavy  glass  or  fine  wire  gauze  screen 
placed  between  the  pipette  and  the  operator,  the  spark 
passed  between  the  spark  wires,  and  the  contraction 
in  volume  noted.  The  screen  shotild  never  be  omitted, 
as  serious  accidents  may  occur  thereby.  The  oxygen  is 
represented  by  one  third  of  the  contraction.  For  very 
accurate  work  the  sum  of  the  combustible  gases  should 
be  but  one  sixth  that  of  the  non-combustible  gases, 
otherwise  some  nitrogen  will  burn  and  high  results  will 
be  obtained;  *  that  is,  (H  +  O)  :  (N  +  H)  ::  i  :  6. 

II.    ANALYSIS   OF   ILLUMINATING-GAS. 

100  cc.  of  gas  are  measured  from  the  bottle  contain- 
ing the  sample  into  the  burette. 

Determination  of  Carbon  Dioxide. — The  burette 
is  connected  with  the  pipette  containing  potassium 

*  This  is  shown  in  the  work  of  Gill  and  Hunt,  J.  Am.  Chem. 
Soc.,  17,  987  (1895). 


APPARATUS.  41 

hydrate  and  the  gas  passed  into  it  with  shaking  until 
no  further  diminution  in  volume  takes  place. 

Illuminants,  CwHa(/ ,  CMH2W  6  Series. — The  rubber 
connectors  are  'carefully  dried  out  with  filter-paper,  a 
dry  capillary  used,  and  the  gas  passed  into  the  pipette 
containing  fuming  sulphuric  acid  and  allowed  to  stand, 
with  occasional  passes  to  and  fro,  for  forty-five  minutes. 
On  account  of  the  extremely  corrosive  nature  of  the 
absorbent  it  is  not  advisable  to  shake  the  pipette,  as 
in  case  of  breakage  a  serious  accident  might  occur. 
For  Boston  gas  this  is  sufficient,  although  with  richer 
gases  check  readings  to  0.2  cc.  should  be  obtained. 
It  is  then  passed  into  potassium  hydrate,  as  in  the 
previous  determination,  to  remove  any  sulphurous  acid 
which  may  have  been  formed  and  any  sulphuric 
anhydride  vapor,  these  having  a  higher  vapor  tension 
than  water.  The  difference  between  this  last  reading 
and  that  after  the  absorption  of  the  carbon  dioxide 
represents  the  volume  of  *'  illuminants  "  or  "heavy 
hydrocarbons  ' '  present. 

As  has  already  been  stated,  page  23,  saturated  bromine 
water  may  replace  the  fuming  sulphuric  acid.  Fuming 
nitric  acid  is  not  recommended,  as  it  is  liable  to  oxidize 
carbonic  oxide. 

Oxygen. — This  is  absorbed,  as  in  the  analysis  of 
air,  by  potassium  or  sodium  pyrogallate. 

Carbonic  Oxide. — The  gas  is  now  passed  into  am- 
moniacal  cuprous  chloride,  until  the  reading  is  constant 
to  0.2  cc.  ;  it  is  then  passed  into  a  second  pipette, 
which  is  fresh,  and  absorption  continued  until  constant 
readings  are  obtained. 


42  GAS  AND  FUEL  ANALYSIS. 

For  very  accurate  work  the  gas  should  be  absorbed  in 
a  U  tube  of  iodic  anhydride  heated  to  150°.  Extreme 
care  must  be  taken  to  prevent  contact  of  the  gas  with 
sulphur,  organic  matter,  as  vaseline  and  rubber,*  as  the 
anhydride  is  readily  reduced.  The  reaction  is 


The  diminution  in  volume  represents  the  carbonic  oxide; 
or  the  iodine  can  be  determined  in  the  usual  way  with 
thiosulphate. 

The  volume  of  air  contained  in  the  tube  should  be 
corrected  for  as  follows:  One  end  of  the  tube  is  plugged 
tightly  and  the  other  end  connected  with  the  gas  burette 
partly  filled  with  air.  A  bath  of  water  at  9°  C.  is  placed 
around  the  U-tube  and  the  reading  of  the  air  in  the  gas 
burette  recorded  when  constant;  the  bath  is  now  heated 
to  ico°  and  the  burette  reading  again  recorded  when 
constant.  The  increase  in  reading  represents  one  third 
the  volume  of  the  U-tube,  273  :  273  +  (100  —  9)  :  :3  :4- 

Methane  and  Hydrogen.  —  (a)  Hinman's  Method.^ 
—  The  gas  left  from  the  absorption  of  carbonic  oxide 
is  passed  into  the  large  explosion  pipette.  About  half 
the  requisite  quantity  of  oxygen  (40  cc.)  necessary 
to  burn  the  gas  is  now  added,  mercury  introduced 
through  the  T  in  the  connector  sufficient  to  seal  the 
capillary  of  the  explosion  pipette,  all  rubber  connectors 
carefully  wired,  the  pinch-cocks  closed,  and  the  pipette 
cautiously  shaken.  A  screen  of  heavy  glass  or  fine 
wire  gauze  is  interposed  between  the  operator  and  the 

•    *  Morgan  &  McWhorter,  J.  Am.  Chem.  Soc.,  22,  14  (1900). 
f  Gill  and  Hunt,  J.  Am.  Chem.  Soc.,  17,  987  (1895). 


APPARA  TUS.  43 

apparatus,  the  explosion  wires  are  connected  with  the 
induction  coil,  a  spark  passed  between  them  and  the 
pinch-cocks  opened,  sucking  in  the  remainder  of  the 
oxygen.  The  capillary  is  again  sealed  with  mercury, 
the  stop-cock  opened  and  closed,  to  bring  the  contents 
of  the  pipette  to  atmospheric  pressure,  and  the  explo- 
sion repeated  as  before,  and  the  stop-cock  opened. 

It  may  be  found  expedient,  to  increase  the  inflamma- 
bility of  the  mixture,  to  in  Deduce  5  cc.  of  "  detonating- 
gas,  ' '  the  hydrolytic  mixture  of  hydrogen  and  oxygen. 
The  gas  in  the  pipette  containing  carbon  dioxide, 
oxygen,  and  nitrogen  is  transferred  to  the  mercury 
burette  and  accurately  measured.  The  carbon  dioxide 
resulting  from  the  combustion  of  the  marsh-gas  is 
determined  by  absorption  in  potassium  hydrate ;  to 
show  the  presence  of  an  excess  of  oxygen,  the  amount 
remaining  is  determined  by  absorption  with  potassium 
pyrogallate. 

The  calculation  is  given  on  page  44.  For  very 
accurate  work  a  second  analysis  should  be  made, 
making  successive  explosions,  using  the  percentages  of 
methane  and  hydrogen  just  found  as  a  basis  upon  which 
to  calculate  the  quantity  of  oxygen  to  be  added  each 
time.  The  explosive  mixture  should  be  so  proportioned 
that  the  ratio  of  combustible  gas  (i.e.,  CH4,  H  and  O) 
is  to  the  gases  which  do  not  burn  (i.e.,  N  and  the 
excess  of  CH4  and  H)  as  100  is  to  about  50  (from  26 
to  64);*  otherwise  the  heat  developed  is  so  great  as 
to  produce  oxides  of  nitrogen,  which,  being  absorbed 

*  Bunsen,  Gasometrische  Methoden,  26.  ed.,  p.  73  (1877). 


44  GAS  AND    FUEL   ANALYSIS. 

in  the  potassium  hydrate,  would  affect  the  determina- 
tion of  both  the  methane  and  the  hydrogen.  The 
oxygen  should  preferably  be  pure,  although  commer- 
cial oxygen,  the  purity  of  which  is  known,  can  be 
used ;  the  oxygen  content  of  the  latter  should  be  tested 
from  time  to  time,  especially  with  different  samples. 

(/?)  Hempel' s  Method* — From  12  to  15  cc.  of  the 
gas  are  measured  off  into  the  burette  (e.g.,  13.2  cc.) 
and  the  residue  is  passed  into  the  cuprous  chloride 
pipette  for  safe  keeping.  That  in  the  burette  is  now 
passed  into  the  small  explosion  pipette;  a  volume  of 
air  more  than  sufficient  to  burn  the  gas,  usually  about 
85  cc.,  is  accurately  measured  and  also  passed  into  the 
explosion  pipette,  and  in  so  doing  water  from  the 
burette  is  allowed  to  partially  fill  the  capillary  of  the 
pipette  and  act  as  a  seal.  The  rubber  connectors  upon 
the  capillaries  of  the  burette  and  pipette  are  carefully 
wired  on,  both  pinch-cocks  shut,  and  the  stop-cock 
closed.  The  pipette  is  cautiously  shaken,  the  screen 
interposed,  the  explosion  wires  connected  with  the 
induction  coil,  a  spark  passed  between  them,  and  the 
stop-cock  immediately  opened.  The  gas  in  the  pipette, 
containing  carbon  dioxide,  oxygen,  and  nitrogen,  is 
transferred  to  the  burette,  accurately  measured,  by 
reading  immediately,  to  prevent  the  absorption  of  car- 
bon dioxide,  and  carbon  dioxide  and  oxygen  deter- 
mined in  the  usual  way. 

Calculation. — (a)  Hinmarfs  Method. — 56.2  cc.  of 
gas  remained  after  the  absorptions;  77.4  cc.  of  oxygen 
were  introduced,  giving  a  total  volume  of  133.6  cc. 

*  Hempel,  Gas  Analytische  Methoden,  3d  ed.,  p.  245  (1901). 


APPARATUS. 


45 


Residue  after  explosion 4-6-9  cc. 

Residue  after  COa  absorption 28.2    " 

Carbon  dioxide  formed 18.7    " 

Contraction 133.6  —  46.9=    86.7   " 

Residue  after  O  absorption 25.6   " 

Oxygen   in  excess,  28.2  —  25.6  =      2.6   " 

The  explosion  of   marsh-gas  or  methane  is  repre- 
sented by  the  equation* 


CH4 


o,    = 


CO, 


H.O 


From  this  it  is  evident  that  the  volume  of  carbon 
dioxide  is  equal  to  the  volume  of  methane  present; 
therefore  in  the  above  example,  in  the  56.2  cc.  of  gas 
burned  there  were  18.7  cc.  methane. 

The  total  contraction  is  due  (i)  to  the  disappearance 
of  oxygen  in  combining  with  the  hydrogen  of  the 
methane,  and  (2)  to  the  union  of  the  free  hydrogen 
with  oxygen.  The  volume  of  the  methane  having 
been  found,  (i)  can  be  ascertained  from  the  equation 
above,  equals  twice  the  volume  of  the  methane;  hence 

86.7  -  (2  X  18.7)  =  49.3  cc., 

contraction  which  is  due  to  the  combustion  of  hydrogen. 
This  takes  place  according  to  the  following  reaction :  * 


O,     = 


H.O 


H,0 


*  HaO  being  as   steam   at    100°  C.     At  ordinary  temperatures 
this  is  condensed,  giving  rise  to  "  total  contraction." 


46  GAS  AND    FUEL  ANALYSIS. 

Hydrogen  then  requires  for  its  combustion  half  its 
volume  of  oxygen,  hence  this  49.3  cc.  represents  a 
volume  of  hydrogen  with  J  its  volume  of  oxygen,  or 
J  volumes;  hence  the  volume  of  hydrogen  is  32.9  cc. 

(£)  Hemper s  Method. — Of  the  82  cc.  of  gas  remain- 
ing after  the  absorptions,  13.2  cc.  were  used  for  the 
explosion  ;  86.4  cc.  air  introduced  giving  a  total  volume 
of  99.6  cc. 

Residue  after  explosion 78.0  cc. 

Residue  after  CO3  absorption 73.2    4< 

Carbon  dioxide  formed 4.8  " 

Contraction 99.6  —  78.0=  21.6  " 

Residue  after  O  absorption 70.2  " 

Oxygen  in  excess.  .73.2  —  70.2  =  3.0  " 

The  carbon  dioxide  being  equal  to  the  methane 
present,  in  the  13.2  cc.  of  gas  burned,  there  were 
4.8  cc.  of  methane.  The  volume  of  methane  is  found 
by  the  proportion  13.2  :  82  ::  4.8  :  x,  whence  x  ~ 
29.8  cc. 

The  hydrogen  is  calculated  similarly. 

The  following  method  of  calculation  may  be  substi- 
tuted for  that  on  page  43  :  Let  m  =  methane,  h  = 
hydrogen,  c  =  total  contraction,  and  O  =  oxygen 
actually  used ;  then 

2m  +  |  =  O 
and 

2m  +  $  =  c, 


APPARATUS.  47 

whence 


and 

h  =  c  -  O. 

The  explosion  can  also  be  made  after  the  absorption 
of  oxygen  and  thus  the  troublesome  absorption  of  car- 
bonic oxide  avoided.  The  calculation  is  then,  if  C  = 
carbonic  oxide,  K  =  CO,  formed  : 


(I) 


K  =  C  +  m,     .     .....     (2) 

V  =  C  +  m  +  h;       ....     (3) 


whence 

h  =  V  -  K, 


- 

3  3 


2K  2C 


Another  method  for  the  estimation  of  hydrogen  is 
by  absorption  with  palladium  sponge  ;  *  it,  however, 
must  be  carefully  prepared,  and  it  is  the  author's 
experience  that  one  cannot  be  sure  of  its  efficacy  when 
it  is  desired  to  make  use  of  it.  A  still  better  absorbent 
of  hydrogen  t  is  a  I  per  cent  solution  of  palladous 

*  Hempel,  Berichte  deutsch.  ch.  Gesell.,  12,  636  and  1006(1879). 
f  Campbell  and  Hart,  Am.  Chem.  J.,  18,  294  (1896). 


4  GAS  AND   FUEL  ANALYSIS. 

chloride  at  50°  C.  ;  when  fresh  this  will  absorb  20—50 
cc.  of  hydrogen  in  ninety  minutes.  A  proportionately 
longer  time  is  required  if  more  hydrogen  be  present  or 
the  solution  nearly  saturated.  The  methane  could 
then  be  determined  by  explosion  or  by  mixing  with 
air  and  passing  to  and  fro  over  a  white-hot  platinum 
spiral-  in  a  tubulated  pipette  called  the  grisoumeter  * 
(grisou  —  methane). 

Nitrogen. — There  being  no  direct  and  convenient 
method  for  its  estimation  with  this  apparatus,  the  per- 
centage is  obtained  by  finding  the  difference  between 
the  sum  of  all  the  percentages  of  the  gases  determined 
and  100  per  cent. 

New  f  determines  nitrogen  in  illuminating-gas  di- 
rectly after  the  method  of  Dumas  in  organic  sub- 
stances; 150  cc.  of  gas  are  used,  the  hydrocarbons 
partially  absorbed  by  fuming  sulphuric  acid  and  the 
remainder  burned  in  a  combustion  tube  with  copper 
oxide;  the  carbon  dioxide  is  absorbed  and  the  residual 
nitrogen  collected  and  measured. 

Accuracy  and  Time  Required. — For  the  absorp- 
tions the  apparatus  is  accurate  to  O.  I  cc.  ;  for  explosions 
by  Hinman's  method  J  the  methane  can  be  determined 
within  0.2  per  cent,  the  hydrogen  within  0.3  per  cent; 
by  Hempel's  method  within  I  per  cent  for  the  methane 
and  7.5  per  cent  for  the  hydrogen.  The  time  required 
for  the  analysis  of  illuminating-gas  is  from  three  to 
three  and  one-half  hours ;  for  air,  from  fifteen  to  twenty 
minutes. 

*  Winkler,  Fres.  Zeit.,  28,  269  and  288. 
f  J.  Soc.  Chem.  Ind.,  n,  415  (1892). 
\  Gill  and  Hunt,  loc  cit. 


APPARA  TVS.  49 

Notes. — The  object  in  filling  the  capillaries  of  the 
explosion  pipettes  with  water  or  mercury  before  the 
explosion  is  to  prevent  the  bursting  of  the  rubber  con- 
nectors on  them.  With  mercury  this  is  effected  by 
introducing  it  through  the  T  joint  in  the  connector. 
After  testing  for  oxygen  with  the  pyrogallate  a  small 
quantity  of  dilute  acetic  acid  is  sucked  into  the  burette 
to  neutralize  any  alkali  which  by  any  chance  may  have 
been  sucked  over  into  it.  The  acid  is  rinsed  out  with 
water  and  this  forced  out  by  mercury  before  the  burette 
is  used  again. 

The  water  in  the  burette  should  be  saturated  with 
the  gas  which  is  to  be  analyzed — as  illuminating-gas 
• — before  beginning  an  analysis.  The  reagents  in  the 
pipettes  should  also  be  saturated  with  the  gases  for 
which  they  are  not  the  reagent.  For  example,  the 
fuming  sulphuric  acid  should  be  saturated  with  oxygen, 
carbon  monoxide,  methane,  hydrogen,  and  nitrogen; 
this  is  effected  by  making  a  blank  analysis  using 
illuminating-gas. 

The  method  of  analysis  of  the  residue  after  the 
absorptions  have  been  made  by  explosion  is  open  to 
two  objections:  1st,  the  danger  of  burning  nitrogen  by 
the  violence  of  the  explosion;  and  2d,  the  danger  of 
breakage  of  the  apparatus  and  possible  injury  to  the 
operator.  These  may  be  obviated  by  employing  the 
apparatus  of  Dennis  and  Hopkins,*  which  is  practically 
a  grisoumeter  with  mercury  as  the  confining  liquid ;  or 
that  of  Jager,  t  who  burns  the  gases  with  oxygen  in  a 

*  J.  Am.  Chem.  Soc.,  21,  398  (1899). 

f  J.  f.  Gasbeleuchtung,  41,  764.  Abstr.  J.  Soc.  Chem.  Ind., 
17,  1190(1898). 


50  GAS  AND    FUEL   ANALYSIS. 

hard-glass  tube  filled  with  copper  oxide.  By  heating 
to  250°  C.  nothing  but  hydrogen  is  burned;  higher 
heating  of  the  residue  burns  the  methane.  Or  the  mix- 
ture of  oxygen  and  combustible  gases,  bearing  in  mind 
the  ratio  mentioned  at  the  bottom  of  page  43-  can  be 
passed  to  and  -fro  through  Drehschmidt's  *  capillary 
heated  to  bright  redness.  This  consists  of  a  platinum 
tube  20  cm.  long,  2  mm.  thick,  1.7  mm.  bore,  filled  with 
three  platinum  or  palladium  wires.  The  ends  of  the  tube 
are  soldered  to  capillary  brass  tubes  and  arranged  so 
that  these  can  be  water  cooled.  It  is  inserted  between 
the  burette  and  a  simple  pipette,  mercury  being  the  con- 
fining liquid  in  both  cases.  The  air  contained  in  the 
tube  can  be  determined  as  in  the  case  of  the  tube  contain- 
ing iodic  anhydride,  p.  42. 

To  the  method  of  explosion  by  the  mixture  of  an 
aliquot  part  of  the  residue  with  air,  method  (b),  there 
is  the  objection  that  the  carbon  dioxide  formed  is  meas- 
ured over  water  in  a  moist  burette,  giving  abundant 
opportunities  for  its  absorption,  and  that  the  errors  in 
anylysis  are  multiplied  by  about  six,  in  the  example 

by 


*  Ber.  d.  deut.  chem.  Gesell.  21,  3342  (1888). 


CHAPTER  VI. 

REAGENTS  AND  ARRANGEMENT  OF  THE 
LABORATORY. 

THE  reagents  used  in  gas-analysis  are  comparatively 
few  and  easily  prepared. 

Hydrochloric  Acid,  Sp.  gr.  i.io. — Dilute  "muri- 
atic, acid  "  with  an  equal  volume  of  water.  In  addi- 
tion to  its  use  for  preparing  cuprous  chloride,  it  finds 
employment  in  neutralizing  the  caustic  solutions  which 
are  unavoidably  more  or  less  spilled  during  their  use. 

Fuming  Sulphuric  Acid. — Saturate  "  Nordhausen 
oil  of  vitriol  "  with  sulphuric  anhydride.  Ordinary 
sulphuric  acid  may  be  used  instead  of  the  Nordhausen  ; 
in  this  case  about  an  equal  weight  of  sulphuric  an- 
hydride will  be  necessary.  Absorption  capacity ',  I  cc. 
absorbs  8  cc.  of  ethene  (ethylene). 

Acid  Cuprous  Chloride. — The  directions  given  in 
the  various  text-books  being  troublesome  to  execute, 
the  following  method,  which  is  simpler,  has  been 
found  to  give  equally  good  results.  Cover  the  bottom 
of  a  two-liter  bottle  with  a  layer  of  copper  oxide  or 
"  scale  "  f  in.  deep,  place  in  the  bottle  a  number  of 
pieces  of  rather  stout  copper  wire  reaching  from  top 
to  bottom,  sufficient  to  make  a  bundle  an  inch  in 
diameter,  and  fill  the  bottle  with  common  hydrochloric 


52  GAS  AND   FUEL   ANALYSIS. 

acid  of  1. 10  sp.  gr.  The  bottle  is  occasionally  shaken, 
and  when  the  solution  is  colorless,  or  nearly  so,  it  is 
poured  into  the  half-liter  reagent  bottles,  containing 
copper  wire,  ready  for  use.  The  space  left  in  the 
stock  bottle  should  be  immediately  filled  with  hydro- 
chloric acid  (i.io  sp.  gr.). 

By  thus  adding  acid  or  copper  wire  and  copper 
oxide  when  either  is  exhausted,  a  constant  supply  of 
this  reagent  may  be  kept  on  hand. 

The  absorption  capacity  of  the  reagent  per  cc.  is, 
according  to  Winkler,  15  cc.  CO;  according  to 
Hempel  4  cc.  The  author's  experience  with  Orsat's 
apparatus  gave  I  cc. 

Care  should  be  taken  that  the  copper  wire  does  not 
become  entirely  dissolved  and  that  it  extend  from  the 
top  to  the  bottom  of  the  bottle;  furthermore  the 
stopper  should  be  kept  thoroughly  greased  the  more 
effectually  to  keep  oat  the  air,  which  turns  the  solution 
brown  and  weakens  it. 

Ammoniacal  Cuprous  Chloride. — The  acid  cu- 
prous chloride  is  treated  with  ammonia  until  a  faint 
odor  of  ammonia  is  perceptible;  copper  wire  should 
be  kept  in  it  similarly  to  the  acid  solution.  This 
alkaline  solution  has  the  advantage  that  it  can  be 
used  when  traces  of  hydrochloric  acid  vapors  might 
be  harmful  to  the  subsequent  determinations,  as,  for 
example,  in  the  determination  of  hydrogen  by  absorp- 
tion with  palladium.  It  has  the  further  advantage 
of  not  soiling  mercury  as  does  the  acid  reagent. 

Absorption  capacity,  I  cc.  absorbs  I  cc.  CO. 

Cuprous  chloride  is  at  best  a  poor  reagent  for  the 
absorption  of  carbonic  oxide;  to  obtain  the  greatest 


REAGENTS  AND    LABORATORY.  53 

accuracy  where  the  reagent  has  been  much  used,  the 
gas  should  be  passed  into  a  fresh  pipette  for  final 
absorption,  and  the  operation  continued  until  two 
consecutive  readings  agree  exactly.  The  compound 
formed  by  the  absorption — possibly  Cu,COCl, — is  very 
unstable,  as  carbonic  oxide  may  be  freed  from  the 
solution  by  boiling  or  placing  it  in  vacuo ;  even  if  it 
be  shaken  up  with  N2,  the  gas  is  given  off,  as  shown 
by  the  increase  in  volume  and  subsequent  diminution 
when  shaken  with  fresh  cuprous  chloride. 

Hydrogen. — A  simple  and  effective  hydrogen  gen- 
erator can  be  made  by  joining  two  six-inch  calcium 
chloride  jars  by  their  tubulatures.  Pure  zinc  is  filled 
in  as  far  as  the  constriction  in  one,  and  the  mouth 
closed  with  a  rubber  stopper  carrying  a  capillary  tube 
and  a  pinch-cock.  The  other  jar  is  filled  with 
sulphuric  acid  I  :  5  which  has  been  boiled  and  cooled 
out  of  access  of  air.  The  mouth  of  this  jar  is  closed 
with  a  rubber  stopper  carrying  one  of  the  rubber  bags 
used  on  the  simple  pipettes. 

Mercury. — The  mercury  used  in  gas  analysis  should 
be  of  sufficient  purity  as  not  to  "  drag  a  tail "  when 
poured  out  from  a  clean  vessel.  It  may  perhaps  be 
most  conveniently  cleaned  by  the  method  of  J.  M. 
Crafts,  which  consists  in  drawing  a  moderate  stream 
of  air  through  the  mercury  contained  in  a  tube  about 
3  feet  long  and  \\  inches  internal  diameter.  The  tube 
is  supported  in  a  mercury-tight  V-shaped  trough,  of 
size  sufficient  to  contain  the  metal  if  the  tube  breaks, 
one  end  being  about  3  inches  higher  than  the  other. 
Forty-eight  hours'  passage  of  air  is  sufficient  to  purify 
any  ordinary  amalgam.  The  mercury  may  very  well 


54  GAS  AND   FUEL   ANALYSIS. 

be  kept  in  a  large  separatory  funnel  under  a  layer  of 
strong  sulphuric  acid. 

Fallacious  Chloride. — 5  grams  palladium  wire  are  dis- 
solved in  a  mixture  of  30  cc.  hydrochloric  and  2  cc.  nitric 
acid,  this  evaporated  just  to  dryness  on  a  water-bath,  re- 
dissolved  in  5  cc.  hydrochloric  acid  and  25  cc.  water,  and 
warmed  until  solution  iscomplete.  It  is  diluted  to  750  cc. 
and  contains  about  one  per  cent  of  palladous  chloride.  It 
will  absorb  about  two  thirds  of  its  volume  of  hydrogen. 

Phosphorus. — Use  the  ordinary  white  phosphorus 
cast  in  sticks  of  a  size  suitable  to  pass  through  the 
opening  of  the  tubulated  pipette. 

Potassium  Hydrate. — (a)  For  carbon  dioxide  de- 
termination, 500  grams  of  the  commercial  hydrate  is 
dissolved  in  I  liter  of'  water. 

Absorption  capacity,  I  cc.  absorbs  40  cc,  CO2. 

(b)  For  the  preparation  of  potassium  pyrogallate 
for  special  work,  120  grams  of  the  commercial  hydrate 
is  dissolved  in  100  cc.  of  water. 

Potassium  Pyrogallate. — Except  for  use  with  the 
Orsat  or  Hempel  apparatus,  this  solution  should  be 
prepared  only  when  wanted.  The  most  convenient 
method  is  to  weigh  out  5  grams  of  the  solid  acid  upon 
a  paper,  pour  it  into  a  funnel  inserted  in  the  reagent 
bottle,  and  pour  upon  it  loocc.  of  potassium  hydrate 
(a)  or  (&).  The  acid  dissolves  at  once,  and  the  solution 
is  ready  for  use. 

If  the  percentage  of  oxygen  in  the  mixture  does 
not  exceed  28,  solution  (a)  may  be  used  ;*  if  this 
amount  be  exceeded,  (b)  must  be  employed.  Other- 

*  Clowes,  Jour.  Soc.  Chem.  Industry,  15,  170.  Anderson,  J.  I.  and 
Eng.  Chem.,  7,  595  (1915),  recommends  a  solution  of  15  grm.  pyrogallol 
in  100  cc.  KOH  sp.  gr.  1.55. 


REAGENTS  AND  LABORATORY.  55 

wise  carbonic  oxide  may  be  given  off  even  to  the  extent 
of  6  per  cent. 

Attention  is  called  to  the  fact  that  the  use  of  potassium 
hydrate  purified  by  alcohol  has  given  rise  to  erroneous 
results. 

Absorption  capacity,  i  cc.  absorbs  2  cc.  O. 

Sodium  Hydrate. — Dissolve  the  commercial  hydrate 
in  three  times  its  weight  of  water.  This  may  be  employed 
in  all  cases  where  solution  (a)  of  potassium  hydrate  is 
used.  The  chief  advantage  in  its  use  is  its  cheapness. 
Anderson*  states  that  it  is  not  practicable  to  use  it  for 
pyrogallol;  this  is  at  variance  with  the  experiments  of 
Wehl  t,  Berthelot  {  and  the  author.  It  has  been  so 
used  in  the  author's  laboratory  for  more  than  twenty- 
five  years,  the  absorption  is  rapid  and  complete.  Sodium 
pyrogallate  is,  however,  a  trifle  slower  in  action  than  the 
corresponding  potassium  salt. 

/ 
ARRANGEMENT  OF  THE  LABORATORY. 

The  room  selected  for  a  laboratory  for  gas-analysis 
should  be  well  lighted,  preferably  from  the  north  and 
east.  To  prevent  changes  in  temperature  it  should 
be  provided  with  double  windows,  and  the  method  of 
heating  should  be  that  which  will  give  as  equable  a 
temperature  as  possible.  In  the  author's  laboratory, 
instead  of  the  usual  tables,  shelves  are  used,  18  inches 
wide  and  ij  inches  thick,  best  of  slate  or  soapstone, 
firmly  fastened  to  the  walls,  30  inches  from  the  floor; 
the  Orsat  apparatus,  when  not  in  use,  may  be  sus- 
pended from  these.  The  reagents  are  contained  in 

*  Loc.  cit.  t  Ber.  14,  2659  (1881). 

t  Ann.  chim.  phys.,  15,  294  (1898). 


56  GAS  AND   FUEL   ANALYSIS. 

half-liter  bottles  fitted  with  rubber  stoppers,  placed 
upon  a  central  table  convenient  to  all.  Here  are 
found  scales,  funnels  and  graduates  for  use  in  making 
up  reagents.  Distilled  water  is  piped  around  to  each 
place  by  -J-inch  tin  pipe  and  ^-inch  rubber  tubing 
from  a  £-inch  "main,"  being  supplied  at  the  tern- 


FIG.  14. — MUENCKE'S  ASPIRATOR. 

perature  of  the  room  from  bottles  placed  about  six 
feet  above  the  laboratory  shelves.  A  supply  of  a 
gallon  per  day  per  student  should  be  provided. 

At  the  right  of  each  place  is  fixed  a  sand-glass  of 
cylindrical  rather  than  conical  form,  graduated  to 
minutes  for  the  draining  of  the  burettes.  The  "egg- 
timers  "  found  in  kitchen-furnishing  stores  serve  the 
purpose  admirably. 


REAGENTS  AND  LABORATORY. 


57 


"  Unknown  gases"  for  analysis  are  best  contained 
in  a  Muencke  double  aspirator,  Fig.  14,  where  they 
can  be  thoroughly  mixed  before  distribution  and  con- 
veyed by  a  pipe  to  the  central  table. 

Finally,  the  laboratory  should  contain  a  stone-ware 
sink  provided  with  an  efficient  trap  of  the  same 
material,  to  prevent  mercury  from  being  carried  into 
and  corroding  the  lead  waste-pipes. 

Drawers  should  be  provided  with  compartments  for 
various  sizes  of  rubber  connectors,  pinchcocks,  glass 
tubing,  stoppers  and  fittings,  and  tools.  When  work- 
ing with  the  Orsat  apparatus  alone,  three  feet  of  shelf 
space  may  be  allowed  to  each  student;  when  using  this 
with  another,  as,  for  example,  the  Bunte,  another 
foot  should  be  added. 

The  course  which  the  writer  has  been  in  the  habit 
of  giving  to  the  Mechanical  and  Electrical  Engineers 
embraces  two  exercises  in  the  laboratory  of  two  hours 
each,  supplemented  with  four  hours  of  lectures.  The 
students  in  the  laboratory  make  an  analysis  of  air  and 
an  "unknown"  furnace-gas,  take  and  analyze  an 
actual  sample  of  chimney-gas,  and  make  the  calculation 
of  heat  lost  and  air  used.  In  the  lectures,  the  subject 
of  gas-analysis  and  its  other  applications,  and  of  fuels, 
their  origin,  description,  preparation,  analysis,  and 
determination  of  heating  value,  are  described. 


CHAPTER    VII. 

FUELS—  SOLID,   LIQUID,  AND  GASEOUS:  THEIR 
DERIVATION   AND   COMPOSITION. 

The  substances  employed  as  fuels  are: 

a.  SOLID  FUELS.  —  Wood,  peat,  brown,  bituminous 
and   anthracite  coal,   charcoal,    coke,   and   oftentimes 
various   waste  products,  as  sawdust,   bagasse,   straw, 
and  spent  tan. 

b.  LIQUID  FUELS.  —  Crude  petroleum  and  various 
tarry  residues. 

c.  GASEOUS  FUELS.  —  Natural  gas,  producer,     blast- 
furnace, water,  and  illuminating  gas. 

The  essential  constituents  in  all  these  are  carbon  and 
hydrogen;  the  accessory,  oxygen,  nitrogen,  and  ash; 
and  the  deleterious,  water,  sulphur,  and  phosphorus. 

a.  SOLID  FUELS. 

Wood  is  composed  of  three  substances  —  cellulose, 
or  woody  fibre  (C6H10O6)M  ;  the  components  of  the  sap, 
the  chief  of  which  is  lignine,  a  resinous  substance  of 
identical  formula  with  cellulose;  and  water.  The 
formation  of  cellulose  from  carbon  dioxide  and  water 
may  be  represented  by  the  equation 


The  amount  of  water  which  wood  contains  determines 
its  value  as  a  fuel.     This  varies  from  29  per  cent  in  ash 

53 


FUELS— SOLID,  LIQUID,  AND  GASEOUS.          59 

to  50  per  cent  in  poplar;  it  varies  also  with  the  season 
at  which  the  wood  is  cut,  being  least  when  the  sap  is  in 
the  roots — in  December  and  January.  This  difference 
may  amount  to  10  per  cent  in  the  same  kind  of  wood. 

The  harder  varieties  of  wood  make  the  best  fuel,  a 
cord  of  seasoned  hardwood  being  about  equal  to  a  ton 
of  coal.  Yellow  pine,  however,  has  but  half  this 
value;  the  usual  allowance  in  a  boiler-test  is  0.4  the 
value  of  an  equal  weight  of  coal. 

The  ash  of  wood  is  mainly  potassium  carbonate, 
with  traces  of  other  commonly  occurring  substances, 
as  lime,  magnesia,  iron,  silica,  and  phosphoric  acid. 

The  percentage  composition  of  wood  may  be  con- 
sidered as  approximately, 

Water,        Carbon.        Hydrogen.        Oxygen.          Ash.  Sp.  Gr. 

20  39  4.4  35.6  I  0.5.* 

When  burned  it  yields  about  4000  C.  per  kilo,  and 
requires  6  times  its  weight  of  air  or  4.6  cu.  m.  (74.1 
cu.  ft.  per  pound)  for  its  combustion. 

Peat  finds  considerable  application  in  Europe,  and 
is  coming  into  use  in  this  country  in  the  form  of  bri- 
quettes. To  this  end  it  is  reduced  to  a  dry  powder 
and  compressed  into  small  cylindrical  blocks;  it  is 
claimed  to  be  as  efficient  as  coal  at  half  the  price.  It 
is  also  proposed  to  gasify  peat  after  the  mannei  of 
coal.  Peat  is  produced  by  the  slow  decay  under  water 
of  certain  swamp  plants,  more  especially  the  mosses 
(Sphagnaceae),  evolving  methane  (CH4)  (marsh-gas) 
and  carbon  dioxide  (CO,). 

It  contains  considerable  moisture,  from  20  to  50 
per  cent,  and  10  per  cent  even  when  "thoroughly 

*  Mills  &  Rowan,  Fuels,  p.  II. 


60  GAS  AND   FUEL   ANALYSIS. 

dry."  Thirty  per  cent  of  its  available  heat  is  employed 
in  evaporating  this  moisture.  The  high  content  of 
ash,  from  3  to  30  per  cent,  averaging  15  per  cent,  also 
diminishes  its  value  as  a  fuel. 

The  ash  of  peat  differs  from  that  of  wood  in  contain- 
ing little  or  no  potassium  carbonate. 

The  percentage  composition  of  peat  may  be  consid- 
ered as  approximately, 

Water.      Carbon.  Hydrogen.  Oxygen.  Nitrogen.     Ash.       Sp.  Gr- 
German 16.4         41.0         4.3          23.8        2.6         11.9       1.05 

American...    20.8         40.8         4.4  26.6  7.7        — 

Such  peat  is  about  equivalent  to  wood  in  its  heating 
effect,  one  pound  evaporating  from  4.5  to  5  pounds 
of  water. 

Coal. — Geologists  tell  us  that  coal  was  probably 
produced  by  the  decay  under  fresh  water  of  plants 
belonging  principally  to  the  Conifer,  Fern  and  Palm 
families;  these  flourished  during  the  Carboniferous 
Age  to  an  extent  which  they  never  approached  before 
or  since.  Representatives  of  the  last  family,  which 
it  is  thought  produced  most  of  the  coal,  have  been 
found  2  to  4  feet  in  diameter  and  80  feet  in  height. 

By  their  decay,  carbon  dioxide  "  choke-damp," 
marsh-gas  "  fire-damp,"  and  water  were  evolved. 
The  change  might  be  represented  by  the  equation 

6C.H10  0.  =  7CO,  +  3CH,  +  I4H,0  +  CMH20O,.      . 

Cellulose.  Bituminous  Coal. 

Some  idea  of  the  density  of  the  vegetation  and  the 
time  required  may  be  obtained  from  the  fact  that  it 
has  been  calculated  that  100  tons  of  vegetable  matter 
— the  amount  produced  per  acre  per  century — if  com- 
pressed to  the  specific  gravity  of  coal  a,nd  spread  over 


FUELS— SOLID,  LIQUID,  AND    GASEOUS.  6 1 

an  acre  would  give  a  layer  less  than  O.6  of  an  inch 
thick.  Now  four  fifths  of  this  is  lost  in  the  evolution 
of  the  gaseous  products,  giving  as  a  result  an  accumu- 
lation of  one  eighth  of  an  inch  per  century,  or  one  foot 
in  10,000  years.* 

Brown  Coal  or  Lignite  may  be  regarded  as  forming 
the  link  between  wood  and  coal;  geologically  speaking 
it  is  of  later  date  than  the  true  coal.  Most  of  the  coal 
west  of  the  Rocky  Mountains  is  of  this  variety. 

As  its  name  denotes,  it  generally  is  of  brown  color 
— although  the  western  coal  is  black — and  has  a  con- 
choidal  fracture.  It  contains  a  large  quantity  of 
water  when  first  mined,  as  much  as  60  per  cent,  and 
when  "  air-dry  "  from  15  to  20  per  cent.  The  per 
cent  of  ash  is  also  high,  from  I  to  20  per  cent. 

The  average  moisture  and  ash  in  American  lignites 
are  12.75  an<^  6.1  respectively. 

The  percentage  composition  of  brown  coal  may  be 
considered  as  approximately, 

Water.  Carbon.         Hydrogen.  Oxygen  &  Nitrogen.   Ash.  Sp.  Gr. 

German     18.0  50.9  4.6  16.3  10.2  1.3 

Bituminous  Coal. — This  is  the  variety  from  which  all 
the  following  coals  are  supposed  to  have  been  formed, 
by  a  process  of  natural  distillation  combined  with  pres- 
sure. According  to  the  completeness  of  this  process 
we  have  specimens  which  contain  widely  differing  quan- 
tities of  volatile  matter.  This  forms  the  true  basis  for 
the  distinguishing  of  the  varieties  of  coal.  In  ordinary 
bituminous  coal  this  volatile  matter  amounts  to  30  or 
40  per  cent.  Three  varieties  of  bituminous  coal  are 
ordinarily  distinguished,  as  follows: 

*  In  case  the  student  desires  to  follow  in  a  more  extended 
manner  the  geology  of  coal,  reference  may  be  had  to  Le  Conte's 
"  Elements  of  Geology."  ou.  ^tc-4i4,  sd  ed- 


62  GAS  AND   FUEL   ANALYSIS. 

Dry  or  non-caking  —those  which  burn  freely  with  but 
little  smoke  and — as  the  name  denotes — do  not  cake 
together  when  burned.  The  coals  from  Wyoming 
are  an  example  of  this  class. 

Caking — those  which  produce  some  smoke  and  cake 
or  sinter  together  in  the  furnace.  An  example  of 
these  is  the  New  River  and  Connellsville  coal. 

Fat  or  Long-flaming — those  producing  much  flame 
and  smoke  and  do  or  do  not  cake  in  burning;  volatile 
matter  50  per  cent  or  more.  Some  of  the  Nova 
Scotia  coals  belong  to  this  class. 

Bituminous  coal  varies  much  in  its  composition — is 
black  or  brownish  black,  soft,  friable,  lustrous,  and  of 
specific  gravity  of  1.25  to  1.5. 

Moisture  varies  from  0.25  to  8  per  cent,  averaging 
about  5. 

The  percentage  composition  of  bituminous  coal  may 
be  considered  as  approximately,* 

Water.          Carbon.        Hydrogen.        Oxygen.      Nitrogen.        Ash.  Sulphur. 

0.9  77.1  5.2  0.7  1.6  7.6  i.o 

Water.  Volatile  Matter.  Fixed  Carbon.  Ash. 

0.9  27.4  64.1  7.6 

Semi-Bituminous  or  Semi-Anthracite  Coal  is  upon  the 
border-line  between  the  preceding  and  the  following 
variety;  it  is  harder  or  softer  than  bituminous,  contains 
less  volatile  matter  (15  to  20  per  cent),  and  burns 
with  a  shorter  flame.  An  example  of  this  is  the 
Pocahontas  coal. 

The  percentage  composition  of  semi- bituminous  and 
semi-anthracite  coal  may  be  considered  to  be  approxi- 
mately,* 

Water.          Carbon.         Hydrogen.     Oxygen.      Nitrogen.         Ash.          Sulphur. 

0.5  83.0  4.7  4.2  1.3  5.5  0.8 

Water.  Volatile  Matter.  Fixed  Carbon.  Ash. 

Q.5 16.7 77-3 5-5 

*  H    T.  Williams. 


FUELS— SOLID,  LIQUID,  AND    GASEOUS.  63 

Anthracite  Coal  is  the  hardest,  most  lustrous,  and 
densest  of  all  the  varieties  of  coal,  having  a  specific 
gravity  of  1.3  to  i./^S;  it  contains  the  most  carbon 
and  least  hydrogen  and  volatile  matter  (5  to  10  per 
cent).  It  has  a  vitreous  fracture  and  kindles  with 
difficulty,  burning  with  a  feeble  flame,  giving  little  or 
no  smoke  and,  with  sufficient  draft,  an  intense  fire. 
The  Lehigh  coal  is  an  excellent  example  of  this  class. 

The  percentage  composition  of  anthracite  coal  may 
be  considered  as  approximately,* 

Water.          Carbon.       Hydrogen.      Oxygen.      Nitrogen.          Ash.  Sulphur. 

2.0  83.9  2.7  2.8  0.8  7.2  0.6 

Water  Volatile  Matter.  Fixed  Carbon.  Ash. 

2.0  4.3  86.5  7.2 

The  ash  of  coal  \  varies  from  I  to  20  per  cent 
and  is  mainly  clay — silicate  of  alumina — with  lime, 
magnesia,  and  iron.  When  coal  is  burned  it  yields 
from  6100  to  8000  C.  and  requires  about  12  times  its 
weight  of  air,  9.76  cu.  m.  per  kilo  or  156.7  feet  per 
pound.  For  the  greatest  economy  Scheurer-Kestner  J 
found  that  this  should  be  increased  from  50  to  100 
per  cent. 

Charcoal  is  prepared  by  the  distillation  or  smoulder- 
ing  of  wood,  either  in  retorts,  where  the  valuable 
by-products  are  saved,  or  in  heaps.  It  should  be 
jet-black,  of  bright  lustre  and  conchoidal  fracture. 

When  wood  is  charred  in  heaps  only  about  20  per 
cent  of  its  weight  in  charcoal  is  obtained — 48  bushels 
per  cord,  or  about  half  the  percentage  of  carbon. 
When  retorts  or  kilns  are  employed,  the  yield  is  in- 
creased to  30  per  cent,  and  40  per  cent  of  pyroligneous 

*  H.  J.  Williams. 

t  Regarding  the  fusibility  of  coal  ash,  see  Fieldner,  J.  Ind.  and  Eng. 
Chem.,  7,  829  (1915).  \  Jour.  Soc.  Chem.  Ind.,  7,  616. 


64  GAS  AND    FUEL   ANALYSIS. 

acid   of    10  per  cent  strength,  with  4  per  cent  of  tar, 
are  obtained. 

The  percentage  composition  of  wood-charcoal  may  be 
considered  as  approximately, 

Carbon.  Ash.  Sp.  Gr. 

97-0  3.0  0.2 

Coke  is  prepared  by  the  distillation  of  bituminous 
coal  in  ovens;  these  are  of  two  types,  those  in  which 
the  distillation-products  are  allowed  to  escape — the 
"  beehive  "  ovens — and  those  in  which  they  are  care- 
fully saved,  as  the  Otto-Hoffman,  Semet-Solvay, 
Simon-Carves',  and  others. 

The  "  beehive"  ovens  yield  from  50  to  65  per 
cent  of  the  weight  of  the  coal — about  2\  tons.  The 
Otto-Hoffman  ovens  are  long  narrow  thin-walled  re- 
torts 33  by  6  by  1.5  feet,*  regeneratively  heated  by  side 
and  bottom  flues;  the  charge  is  about  6  tons  of  coal, 
and  the  following  percentage  yields  of  by-products 
are  obtained:  coke  70-75,  gas  16  (10  M.  cu.  ft.),  tar 
3.3-5.6,  ammonia  0.3-1.4.1  The  Semet-Solvay  ovens 
differ  from  the  above  in  that  they  are  not  regen- 
eratively heated  and  their  walls  are  thicker,  serving  to 
store  up  the  heat ;  the  yield  of  coke  is  somewhat 
higher — about  80  per  cent.J  The  by-products  ob- 
tained alone  increase  the  value  of  the  output  about 
one  and  one  half  times.  Good  coke  should  possess  a 
cellular  structure,  a  metallic  ring,  contain  practically 
no  impurities,  and  be  capable  of  bearing  a  heavy 
burden  in  the  furnace. 

*  Irwin,  Eng.  Mag.,  Oct.  1901,  abstr.  J.  Am.  Chem.  Soc.,  24,  40. 
f  H.  O.  Hofman,  Tech.  Quar.,  II,  212  (1898). 
j  Pennock,  J.  Am.  Chem.  Soc.,  21,  678  (1899). 


FUELS— SOLID,  LIQUID,  AND    GASEOUS.  6$ 

The  analysis  of  Connellsville  coke  with  the  coal 
from  which  it  is  prepared  is  given  below. 

Water.        Volatile  Matter.      Carbon.          Sulphur.  Ash. 

Coal          1.26  30.1  59.62  0.78  8.23 

Coke        0.03  1.29  89.15  0.084  9.52 

Otto-Hoffman  coke: 

Fixed  Carbon. 

3-7                       1-3                                   86-J  8-9 

Heating  value 7100  C. 

The  Minor  Solid  Fuels. 

Sawdust  and  Spent  Tan-bark  find  occasional  use, 
their  value  depending  upon  the  quantity  of  moisture 
they  contain.  With  57  per  cent  of  moisture  I  pound 
of  tan-bark  gave  an  evaporation  of  4  pounds  of  water. 

Wheat  Straw  finds  application  as  fuel  in  agricul- 
tural districts,  3^  pounds  being  equal  to  I  pound  of 
coal.  Upon  sugar-plantations  the  crushed  cane  or 
Bagasse,  partially  dried,  is  extensively  used  as  a 
fuel.  With  16  per  cent  of  moisture  an  evaporation 
of  2  pounds  of  water  per  pound  of  fuel  has  been 
obtained. 

Briquets/' Patent  Fuel."*— In  Europe  coal  dust  is 
cemented  together  with  some  tarry  binding  material 
and  baked  or  compressed  into  blocks  usually  about 
6X2X1  inches,  which  form  a  favorite  fuel  for  domestic 
purposes.  In  some  cases  they  take  the  form  and  size 
of  a  large  goose  egg,  and  are  called  eggettes:  these  are 
being  made,  among  other  places,  at  Scranton,  Pa.,  and 
withstand  well  the  shocks  incident  to  shipment. 

*  Condition  of  the  Coal  Briquetting  Industry  in  the  United  States, 
E.  W.  Parker,  Bull.  No.  316  U.  S.  Geol.  Survey,  Contributions  to 
Economic  Geology,  1906.  Part  II,  Coal  Lignite  and  Peat,  pp. 
460-485. 


66  GAS   AND  FUEL  ANALYSIS. 

Storage  of  Coal  aud  Spontaneous  Combustion. — 

While  authorities  differ  as  to  the  way  and  manner  in 
which  coal  should  be  stored,  as  regards  height  of  pile, 
number,  size,  and  arrangement  of  ventilating  channels, 
they  are  practically  agreed  that  it  should  always  be 
covered.  Six  months'  exposure  to  the  weather  may  with 
European  coals  cause  a  loss  of  from  10  to  40  per  cent  in 
heating  value,  while  with  Illinois  coals  it  varies  from 
2  to  10  per  cent.*  The  North  German  Lloyd  Steamship 
Company  stores  its  coal  in  a  covered  bin  provided  with 
ventilators,  and  restricts  the  height  of  the  pile  to  8  feet. 
A  large  gas  company  in  a  western  city  also  uses  a  covered 
bin,  with  ventilators  8  inches  square  every  20  feet;  the 
height  of  the  pile  may  be  from  10  to  15  feet.  An  electric 
company  in  the  same  city  f  has  arranged  to  store  14,000 
tons  of  coal  under  water  in  12  pits,  a  steam-shovel  being 
used  to  dig  out  the  coal.  Ventilating  flues  serve  the 
additional  purposes  of  enabling  the  temperature  of  the 
pile  to  be  ascertained  before  ignition  takes  place,  and  as 
a  means  of  introduction  of  either  steam  or  carbonic  acid 
to  extinguish  any  fire  which  may  occur.  All  the  supports 
of  the  bin  in  contact  with  the  coal  should  be  of  brick, 
concrete  or  iron,  and  if  of  hollow  iron,  filled  with  cement. 
The  spontaneous  combustion  of  coal  is  due  primarily 
to  trie  rapid  absorption  of  oxygen  by  the  finely  divided 
coal,  and  to  the  oxidation  of  iron  pyrites,  "coal  brasses," 
occurring  in  the  coal.  The  conditions  favorable  to 
the  process  are: 

*  Parr    and   Hamilton,    Univ.   of  111.,   Bulletin  4,  No.  33,  August, 
1907. 
f  Eng.  and  Min.  Jour.,  September  15,  1906. 


FUELS— SOLID,   LIQUID,    AND   GASEOUS.  67 

First.  A  supply  af  air  sufficient  to  furnish  oxygen,  but 
of  insufficient  volume  to  carry  off  the  heat  generated. 

Second.  Finely  divided  coal,  presenting  a  large  surface 
for  the  absorption  of  oxygen. 

Third.  A  considerable  percentage  of  volatile  matter  in 
the  coal. 

Fourth.     A  high  external  temperature. 

A  method  of  extinguishing  a  fire  in  a  coal  pile  not 
provided  with  ventilators  consists  in  removing  and  spread- 
ing out  the  coal  and  flooding  the  burning  part  with  water. 
Another  method  consists  in  driving  a  number  of  iron  or 
steel  pipes  provided  with  "driven  well  points"  at  the 
place  where  combustion  is  taking  place,  and  forcing 
water  or  steam  through  these  upon  the  fire. 

• 

b.  LIQUID  FUELS. 

These  consist  of  petroleum  and  its  products,  and 
various  tarry  residues  from  processes  of  distillation, 
as  from  petroleum,  coking-ovens,  wood  and  shale. 
Liquid  fuel  possesses  the  advantage  that  it  contains  no 
ash,  is  easily  manipulated,  the  fire  is  of  very  equable 
temperature,  very  hot,  and  practically  free  from  smoke. 

Regarding  the  origin  of  petroleum,  many  theories 
have  been  proposed.  That  of  Engler,*  that  it  was 
formed  by  the  distillation  under  pressure  of  animal  fats 
and  oils,  the  nitrogenous  portions  of  the  animals  pre- 
viously escaping  as  amines,  seems  most  probable;  it 
has  yielded  the  best  results  of  any  hypothesis  when 
tested  upon  an  industrial  scale. 

*  Jour.  Soc.  Chem.  Industry,  14,  648. 


68  GAS   AND   FUEL   ANALYSIS. 

Crude  Petroleum  varies  greatly  in  color  according 
to  the  locality;  it  is  usually  yellowish,  greenish,  or 
reddish  brown,  of  benzine-like  odor,  and  sp.  gr.  of  0.78 
to  0.80.  It  "  flashes"  at  the  ordinary  temperature; 
hence  great  care  should  be  employed  in  its  use  and 
storage.  \ks  percentage  composition  is  shown  below. 

Carbon.  Hydrogen. 

84.0-85.0  I6.O-I5.O 

It  is  more  than  twice  as  efficient  as  the  best  anthra- 
cite coal.  In  practice  14  to  16  pounds  of  water  per 
pound  of  petroleum  have  been  evaporated,  and  an 
efficiency  of  19,000  B.  T.  U.  was  obtained  as  against 
8500  B.  T.  U.  for  anthracite.  In  general  3^  to  4  bar- 
rels of  oil  are  equivalent  to  a  ton  of  good  soft  coal.* 

c.  GASEOUS  FUELS. 

Natural  Gas  is  usually  obtained  when  boring  for 
petroleum  and  consists  mainly  of  methane  and  hydro- 
gen, although  the  percentage  varies  with  the  locality. 
The  Findlay,  Ohio,f  gas  is  of  the  following  composi- 
tion: 

CH4  H  N  O          C2H4        C0a         CO          H2S        Sp.  Gr. 

92.6          2.3          3.5  0.3          0.3         0.3          0.5          0.2          0.57 

Blast-furnace,  Producer,  or  Generator  Gas  is  the 

waste  gas  issuing  from  the  top  of  a  blast-furnace  or  ob- 
tained by  partially  burning  coal  by  a  current  of  air  (pro- 


*  W.  B.  Phillips,  Texas  Petroleum  (1900),  p.  84. 
f  Orton,  Geology  of  Ohio,  vol  vi.  p.  137. 


FUELS—  SOLID,  LIQUID,  AND    GASEOUS.         69 

duced  by  steam)  in  a  special  furnace  —  a  gas-producer  or 
generator.     It  is  mainly  carbonic  oxide  and  nitrogen. 


co        N       co2      H     CH4   o 

Blast-furnace  gas  .....  343  63.7  0.6  1.4 

Gas  from  bitumin.  coal  24.5  46.8  3.7  17.8  6.8  0.4         223 

"       "         "            "  25.0  41.4  4.0  19.4  9.6  0.6 

"       "     anthrac.     "  27.0  57.3  2.5  12.0  1.2     — 

"       "          "          "  17.2  53.1  8.6  18.2  2.4  0.4          140 

"      "          "         "  26.0  47.0  8.0  18.5  0.5     —         145* 

One  ton  of  coal  yields  from  i6of  to  170  thousand 
cubic  feet  of  gas  of  156  to  138  B.T.U.  heating  power,  or 
8  1  to  86  or  even  90  per  cent  of  the  value  of  the  coal. 

Water-gas.  —  If,  instead  of  passing  simply  air  over 
hot  coal,  water-vapor,  or  rather  steam,  be  employed, 
it  is  decomposed,  giving  carbonic  oxide  and  hydrogen, 
according  to  the  equation  H,O  +  C  =  CO  +  H,  ,  and 
the  resulting  mixture  is  called  water-gas.  The  per- 
centage composition,  which  varies  according  to  the  ap- 
paratus and  fuel  employed,  is  about  as  follows: 

CO  H         CH4      C02         N  O        lilts.     Sp.  Gr. 

From  coke....     45.8       45-7       2.0       4.0       2.0      0.5       —        0.57 
From  bit.  coal    34.0       41.9       7.5       5.4       9.2       i.i       0.9        — 

Fischer  {  states  that  I  ton  of  coke  gives  about  36 
thousand  cubic  feet  of  gas,  equivalent  to  42  per  cent 
of  the  value  of  the  coal.  From  I  ton  of  bituminous 
coal  about  51  thousand  cubic  feet  of  gas  of  360  B.T.U. 
heating  power  are  obtained,  or  an  efficiency  of  nearly 
62  per  cent.§ 


*  Suction  gas  producer. 

f  Humphrey,  Jour.   Soc.  Chem.  Industry,  20,    107  (1901);  ibid.,  16, 
522(1897). 

\  Taschenbuch  fur  Feuerungs-Techniker,  p.  27. 
§  Slocum,  J.  Soc.  Chem.  Industry,  16,  420  (1897). 


70  GAS  AND   FUEL   ANALYSIS. 

Coal  or  Illuminating  Gas  was  formerly  produced 
by  the  distillation  of  bituminous  coal;  it  is  at  present 
largely  made  by  the  enriching  of  water-gas.  "Gas- 
oil,"  a  crude  naphtha,  is  blown  into  the  water-gas 
generator  and  changed  to  a  permanent  gas  by  the 
heat.  It  is  of  the  following  composition  : 

H        CH4        CO       CaH4     C02     N       O     Sp.  Gr. 

Coal  gas 47.0     40.5       6.0       4.0     0.5     1.5     0.5     0.4 

Enriched  water-gas     27.9     25.9     25.3     15.0     2.9     3.0     o.o     0.6 

One  ton  of  coal  gives  about  10  thousand  cubic  feet  of 
gas,  or  about  20  per  cent  of  the  heating  value  of  the 
coal. 

Heating  Value  of  these  Gases. 

The  following  table,  mainly  from  Slocum,*  gives  an 
idea  of  rhe  comparative  value  of  the  gases : 


Name  of  Gas. 
Oil  

B.  T.  U.  per      . 
Cu.  Ft.t 

jqCQ 

Yield. 
77  CU     ft 

Air  Required  for 
Combustion 
per  Cu.  Ft. 

080 

per  gal. 

Q.8o 

840-1170 

7OO 

Thousand  Ft. 
per  Ton. 

AO  1 

686 

Coal  

600-625 

IO 

«;  6<; 

332—  ^OO 

Heating  (coke-oven). 

367 
^.12 

5 

C  T 

m6 

D1 
1  60 

•97 

T    oC 

Siemens  producer.... 
Wood  or  peat  

137 
140-145 

170 

*  Slocum,  J.  Soc.  Chem.  Industry.  16,  420  (1897). 

f  Determined  with  the  Junkers  calorimeter. 

|  168-200  gallons  of  "  gas-oil "  are  also  required. 


FUELS— SOLID,    LIQUID,    AND   GASEOUS.  71 

REFERENCES. — Report  of  U.  S.  "Liquid  Fuel"  Board, 
Dept.  of  Navy,  Bureau  of  Steam  Engineering,  Washington, 
1904.  pp.  450. 

Report  on  the  Operations  of  the  Coal-Testing  Plant  of 
the  U.  S.  Geological  Survey  at  St.  Louis,  1904.  Pro- 
fessional Paper,  No.  48,  Parts  I,  II,  and  II.  1906. 

Preliminary  Report  on  the  Operations  of  the  Coal  Testing 
Plant  of  the  U.  S.  Geol.  Survey  at  St.  Louis,  1904. 

Bull.  No.  261,  1905. 

Bull.  No.  261  for  1905. 

Bull.  No.  290,  1906. 

A  Study  of  Four  Hundred  Steaming  Tests,  made  at 
Fuel  Testing  Plant  at  St.  Louis  in  1904,  1905,  1906,  by 
L.  P.  Breckenridge.  Bull.  No.  325,  U.  S.  Geol.  Survey, 
1907. 

The  Burning  of  Coal  -without  Smoke.    D.  T.  Randall. 
Bull.  No.  334,  U.  S.  Geol.  Survey,  1908. 
Barr,  "Boilers  and  Furnaces.'19 
Hodgetts,  "  Liquid  Fuels." 


CHAPTER    VIII. 

METHODS    OF    ANALYSIS     AND     DETERMINATION 
ON   THE    HEATING   VALUE   OF    FUEL. 

SAMPLING. 

A  FEW  representative  lumps  or  shovelfuls  are  taken 
from  each  barrow  or  from  various  points  in  the  pile 
in  boiler  tests.  Shovelfuls  of  coal  should  be  taken  at 
regular  intervals  and  put  into  a  tight  covered  barrel 
or  some  air-tight  receptacle,  and  the  latter  should  be 
placed  where  it  is  protected  from  the  heat  of  the  fur- 
nace.* In  sampling  two  conditions  must  be  observed: 
First,  the  original  sample  should  be  of  considerable  size 
and  thoroughly  representative;  and,  second,  the  quartering 
down  to  an  amount  which  can  be  put  into  a  sealed  "light- 
ning" jar  should  be  carried  out  as  quickly  as  possible 
after  the  sample  is  taken.  Careful  samplings  and  careful 
treatment  of  samples  are  necessary  to  obtain  reliable 
results,  especially  in  the  determination  of  moisture. 
The  lumps  are  coarsely  broken,  and  the  whole  spread 
out  in  a  low  circular  heap.  Diameters  are  drawxi 
at  right  angles  in  it  and  opposite  quarters  taken, 
and  treated  similarly  to  the  whole  sample.  The 
operation  is  continued  until  a  sample  of  a  few  pounds 
is  obtained.  This  is  roughly  crushed  and  samples 
taken  at  different  points  for  the  moisture  determi- 
nation ;  it  is  then  further  quartered  down  until  a 

*  Report  of  Committee  on  Coal  Analysis,  J.  Am.  Chem.  Soc., 
21,  Hi6  et  seq.  (1899). 

72 


FUEL    ANALYSIS— HEATING    VALUE.  73 

sample  of  100  grams  which  passes  a  6o-mesh  sieve  is 
obtained. 

The  methods  employed  in  the  analysis  of  fuels  are 
largely  a  matter  of  convention,  various  methods  giving 
varied  results ;  for  example,  it  is  well-nigh  impossible 
to  obtain  accurately  the  percentage  of  moisture  in 
coal,  as  when  heated  sufficiently  hot  to  expel  the 
water  some  of  the  hydrocarbons  are  volatilized. 

Moisture. — Dry  one  gram  of  coal  in  an  open  cru- 
cible at  IO4°-IO7°  C.  for  one  hour.  Cool  in  a  desic- 
cator and  weigh  covered.  Where  accuracy  is  required, 
determinations  must  also  be  made  on  the  coarsely 
ground  sample ;  this  latter  result  is  to  be  regarded  as 
the  true  amount  and  corrections  applied  to  all  deter- 
minations where  the  powdered  sample  is  used.*  f 

Volatile  Combustible  Matter  and  Coke.*§— Place 
one  gram  of  fresh,  undried  powdered  coal  in  a  platinum 
crucible  having  a  tightly  fitting  cover.  Heat  over  the 
full  flame  of  a  Bunsen  burner  for  seven  minutes  by 
the  watch.  The  crucible  should  be  supported  on  a 
platinum  triangle  with  the  bottom  six  to  eight  centi- 
meters above  the  top  of  the  burner.  The  flame 
should  be  fully  twenty  centimeters  high  when  burning 
free,  and  the  determination  should  be  made  in  a  place 
free  from  drafts.  The  upper  surface  of  the  cover 
should  burn  clear,  but  the  under  surface  should  remain 
covered  with  carbon.  To  find  "Volatile  Combusti- 
ble Matter"  subtract  the  per  cent  of  moisture  from 
the  loss  found  here.  The  residue  in  the  crucible 
minus  the  ash  represents  the  Coke  or  Fixed  Carbon. 

*  Report  of  Committee  on  Coal  Analysis,  loc.+cit. 

f  See  also  an  article  by  Hale,  Proc.  Am.  Soc.  Mech.  Eng.  1896. 

§  Sommermeier,  J.  A.  C.  S.  28,  1002  (1906). 


74  GAS   AND    FUEL  ANALYSIS. 

Certain  non-coking  coals  suffer  mechanical  loss 
from  the  rapid  heating. 

Carbon  and  Hydrogen. — These  are  determined  by 
burning  the  coal  in  a  stream  of  air  and  finally  in 
oxygen,  the  products  of  combustion,  carbon  dioxide 
and  water,  being  absorbed  in  potassium  hydrate  and 
calcium  chloride. 

Apparatus  Required. — Combustion-furnace  similar 
to  that  shown  in  Fig.  15.  Combustion-tube  filled. 


FlG.  15. — COMBUSTION-FURNACE. 

Potash-bulbs  with  straight  chloride  of  calcium  tube 
filled.  Chloride  of  calcium  tube  filled.  Oxygen- 
holder,  drying  and  purifying  apparatus.  Porcelain 
boat,  desiccator,  tongs,  J-inch  rubber  tubing.  Ana- 
lytical balance. 

The  combustion-tube  is  of  hard  glass,  %  inch  in  in- 
ternal diameter  and  36  inches  long,  closed  with  per- 
forated rubber  stoppers.  One  end — called  the  front 
end — is  filled  with  a  layer  of  copper  oxide  12  inches 
long,  held  in  place  by  plugs  of  asbestos  coming 


FUEL  ANALYSIS— HEATING    VALUE.  75 

within  4  inches  of  the  stopper.  In  coals  rich  in  sul- 
phur the  oxide  is  partially  replaced  by  a  layer  of 
chromate  of  lead  2  inches  long.  The  position  of  the 
boat  containing  the  coal  is  immediately  behind  this 
copper  oxide;  behind  the  boat  is  placed  an  oxidized 
copper  gauze  roll,  6  inches  long.  Before  making  the 
combustion,  the  tube  and  contents  should  be  heated 
to  a  dull  red  heat  in  a  stream  of  oxygen  freed  from 
moisture  and  carbon  dioxide  by  the  purifying  appa- 
ratus, to  burn  any  dust  and  dry  the  contents;  it  is 
then  ready  for  use. 

The  potash-bulbs  are  an  aggregation  of  five  bulbs, 
the  three  lowest  filled  with  potassium  hydrate  of  1.27 
sp.  gr.,  the  other  two  serving  as  safety-bulbs,  pre- 
venting the  liquid  from  being  carried  over  into  the 
connectors.  They  should  be  connected  further  with  a 
chloride  of  calcium  tube  to  absorb  any  moisture  carried 
away  by  the  dry  gas.  When  not  in  use  they  should 
be  closed  with  connectors  carrying  glass  plugs.  Before 
weighing  they  should  stand  at  least  fifteen  minutes  in 
the  balance-room  to  attain  its  temperature ;  the  weight 
should  be  to  milligrams  and  without  the  connectors. 

The  chloride  of  calcium  tube  is  of  U  form,  provided 
with  bulbs  for  the  condensation  of  the  water;  the 
granular  calcium  chloride  is  kept  in  place  by  cotton 
plugs,  and  the  stopper  neatly  sealed  in  with  sealing- 
wax.  As  calcium  chloride  may  contain  oxide  which 
would  absorb  the  carbon  dioxide  formed,  a  current  of 
dry  carbon  dioxide  should  be  passed  through  the  tube 
and  thoroughly  swept  out  by  dry  air  before  use. 

The  chloride  of  calcium  tube  like  the  potash-bulbs 
should  be  placed  in  the  balance-room  fifteen  minutes 


76  GAS   AND   FUEL    ANALYSIS. 

before  weighing  and,  if  the  balance-case  be  dry,  may 
be  weighed  without  the  connectors.  It  should  be 
weighed  to  milligrams. 

The  oxygen-holder  may  be  like  the  Muencke  aspi- 
rator, Fig.  14.  The  oxygen  should  be  purified  by 
passing  through  potassium  hydrate  and  over  calcium 
chloride. 

Operation. — The  front  stopper  of  the  combustion 
tube  is  slipped  carefully  upon  the  stem  of  the  chloride 
of  calcium  tube  and  this  connected  to  the  potash- 
bulbs;  02  to  0.3  gram  of  the  coal  is  carefully 
weighed  into  the  porcelain  boat  (to  o.  I  mg.),  the  roll 
removed,  and  the  boat  inserted  behind  the  layer  of 
copper  oxide,  and  the  roll  and  stopper  replaced. 
The  tube  is  now  ready  to  be  heated. 

The  front  of  the  copper  oxide  is  first  heated,  the 
heat  being  gradually  extended  back;  at  this  time  the 
rear  end  of  the  copper  roll  is  heated  and  a  slow  cur^ 
rent  of  purified  air  passed  through.  This  method 
of  gradual  heating  of  the  tube  is  followed  until  the 
layer  of  copper  oxide  and  the  rear  portion  of  the  roll 
are  at  a  dull  red  heat.  Heat  is  now  cautiously  applied 
to  the  coal  and  the  current  of  air  slackened.  The 
volatile  matter  in  the  coal  distils  off,  is  carried  into 
the  layer  of  copper  oxide  and  burned;  the  carbon 
dioxide  formed  can  be  seen  to  be  absorbed  by  the 
potassium  hydrate.  When  this  absorption  almost 
ceases,  oxygen  is  turned  on  and  the  coal  heated  until 
it  glows.  The  stream  of  oxygen  should  be  so  regulated 
as  to  produce  but  two  bubbles  of  carbon  dioxide  in 
the  bulbs  per  second.  If  the  evolution  be  faster,  the 
gas  is  not  absorbed.  When  the  coal  has  ceased  glow- 


FUEL   ANALYSIS— HEATING    VALUE.  77 

ing,  oxygen  is  allowed  to  pass  through  the  apparatus 
until  a  spark  held  at  the  exit  of  the  last  chloride  of 
calcium  tube  (on  the  bulbs)  re-inflames;  the  oxygen  is 
allowed  to  run  for  fifteen  minutes  longer.  The  current 
of  oxygen  is  now  replaced  by  purified  air,  and  the 
heat  moderated  by  turning  down  the  burners  and 
opening  the  fire-clay  tiles;  the  air  is  allowed  to  run 
through  for  twenty  minutes  to  thoroughly  sweep  out 
all  traces  of  carbon  dioxide  and  moisture.  The  bulbs 
and  U  tube  are  disconnected,  stopped  up,  allowed  to 
stand  in  the  balance-room,  and  weighed  as  before. 
The  increase  in  weight  in  the  bulbs  represents  the 
carbon  dioxide  formed;  this  multiplied  by  the  factor 
0.2727  gives  the  carbon.  Similarly  the  increase  in  the 
U  tube,  minus  the  water  due  to  the  moisture  in  the 
coal,  represents  the  water  formed,  one  ninth  of  which 
is  hydrogen. 

Notes. — At  no  time  in  the  combustion  should  any 
water  appear  near  the  copper  roll,  as  it  is  an  indication 
that  the  products  of  combustion  have  gone  backward 
into  the  purifying  apparatus  and  hence  are  lost.  Such 
analyses  should  be  repeated.  Should  moisture  appear 
in  the  front  end,  it  may  be  gently  heated  to  expel  it. 
Both  ends  of  the  tube  should  be  frequently  touched 
with  the  hand  during  the  combustion,  and  should  be 
no  hotter  than  may  be  comfortably  borne,  as  the 
stoppers  give  off  absorbable  gases  when  highly  heated. 
Care  should  be  taken  not  to  heat  the  tube  too  hot, 
fusing  the  copper  oxide  into  and  spoiling  it.  One 
tube  should  serve  for  a  dozen  determinations.  It 
should  not  be  placed  upon  the  iron  trough  of  the 


78  GAS  AND  FUEL  ANALYSIS. 

furnace,  but  upon  asbestos-paper  in  the  trough,  to  pre- 
vent fusion  to  the  latter. 

As.  will  be  seen,  the  execution  of  a  combustion  is  not 
easy,  and  should  only  be  intrusted  to  an  experienced 
chemist.  The  results  are  usually  o.i  per  cent  low  for 
carbon  and  a  similar  amount  high  for  hydrogen. 

Ash. — This  is  determined  by  weighing  the  residue 
left  in  the  boat  after  combustion,  or  by  completely 
burning  one  gram  of  the  coal  contained  in  a  platinum 
dish. 

Nitrogen  is  determined  by  Kjeldahl's  method,  which 
consists  in  digesting  the  coal  with  strong  sulphuric  acid, 
aided  by  potassium  permanganate,  until  nearly  colorless. 
The  nitrogeneous  bodies  are  changed  to  ammonia,  forming 
ammonium  sulphate  and  are  determined  by  rendering 
alkaline  and  distilling  the  solution. 

Sulphur  is  determined  by  Eschka's  method,  con- 
sisting in  heating  for  an  hour  one  gram  of  the  coal  mixed 
with  one  gram  of  magnesium  oxide  and  0.5  grm.  sodium 
carbonate  in  a  platinum  dish  without  stirring,  using  an 
alcohol-lamp,  as  gas  contains  sulphur.  It  is  allowed 
to  cool  and  rubbed  up  with  one  gram  of  ammonium 
nitrate  and  heated  for  5  to  10  minutes  longer.  The 
resulting  mass  is  dissolved  in  200  cc.  of  water  evaporated 
to  150  cc.,  acidified  with  hydrochloric  acid,  filtered,  and 
sulphuric  acid  determined  in  the  filtrate  in  the  usual 
way  with  barium  chloride.  Or  the  washings  of  the 
bomb  calorimeter  may  be  used  (see  liquid  fuels). 

Oxygen  is  determined  by  difference. 

NOTE. — The  foregoing  methods  are  technical,  but  of  sufficient  accuracy 
for  most  purposes.  For  more  accurate  and  later  methods  see  the  Report 
of  the  A.  C.  S.  in  J.  Ind.  and  Eng.  Chem.,  5,  517,  et  seq. 


FUEL  ANALYSIS— HEATING  VALUE.  79 

ANALYSIS   OF   LIQUID   FUELS. 

Carbon  and  Hydrogen. — This  determination  is  made 
as  in  the  case  of  the  solid  fuels,  the  liquid  being  con- 
tained in  a  small  bulb  sealed  for  weighing  to  prevent 
volatilization.  The  stem  is  scratched  and  broken  off 
and  the  bulb  inserted  in  the  combustion  tube  in  place  of 
the  boat.  Extra  care  in  heating  has  to  be  observed  to 
prevent  the  liquid  from  passing  through  unburnt.  For 
thick  or  tarry  oils  having  a  small  quantity  of  volatile 
matter,  the  boat  may  be  used  as  with  solid  fuels. 

Sulphur. — The  method  consists  in  burning  the  oil  in  a 
small  lamp  and  collecting  the  products  of  combustion. 
The  lamp  is  a  miniature  "  oil  lamp  "  made  from  a  3-inch 
test-tube  (weighing  tube)  by  drawing  a  piece  of  weighed 
lamp  wicking  through  a  small  glass  tube  contained  in  the 
stopper.  This  lamp  is  suspended  by  a  wire  from  the 
balance  and  weighed  accurately. 

It  is  lighted  and  hung  under  a  funnel  arranged  so  that 
the  products  of  combustion  are  drawn  by  an  air-pump 
through  a  series  of  two  washing  bottles  containing  satu- 
rated bromine  water.  After  about  a  gram  of  oil  has  been 
burned  (about  1.3  cc.)  the  wick  is  carefully  removed 
without  losing  any  oil,  the  stopper  replaced  and  the  tube 
again  weighed.  The  wick  and  oil  it  contains  are  covered 
with  Eschka's  mixture  and  treated  as  for  the  determina- 
tion of  sulphur  in  coal  (p.  7-8).  The  hydrochloric  acid 
filtrate  is  added  to  the  bromine  solution,  the  bromine 
boiled  out,  the  solution  evaporated  to  about  150  cc.,  and 
the  sulphuric  acid  formed  determined  in  the  usual  way 
with  barium  chloride.  The  oil  burned  is  obviously  the 
weight  of  the  lamp  before  and  after  burning  less  the  weight 


8o  GAS  AND  FUEL  ANALYSIS. 

of  the  dry  wick.  This  treatment  of  the  wick  is  necessary, 
as  Conradson  *  has  found  sometimes  40  per  cent  of  the 
sulphur  in  the  wick. 

By  the  Calorimeter. — After  oil  is  burned  in  the  bomb 
calorimeter  (p.  82),  it  is  thoroughly  washed  out  with 
distilled  water,  and  6-8  cc.  of  HC1  i  :  i  with  a  few  drops 
of  bromine  water  added,  the  solution  heated  to  boiling 
and  filtered;  the  filter  is  washed  free  of  sulphates,  the 
filtrate  made  just  neutral  with  NaOH  or  Na2COs,  i  cc. 
normal  HC1  added  and  the  sulphates  determined  in  the 
usual  way  with  barium  chloride.  If  any  odor  be  detected 
in  the  gases  escaping  from  the  bomb,  the  determination 
must  be  repeated,  using  a  pressure  of  25  atmospheres 
of  oxygen  with  a  bomb  of  400-600  cc.  capacity.  The 
sulphur  is  usually  a  trifle  low. 

Barlow's  |  method  is  excellent,  but  requires  consider- 
able experience  to  carry  out. 

Nitrogen  is  determined  exactly  as  in  the  case  of  solid 
fuels. 

Water  can  be  shown  qualitatively  by  the  eosine  test,J 
by  rubbing  with  a  little  eosine  on  a  glass  plate.  If  water 
be  present  the  oil  will  take  on  a  pink  color.  It  is  quan- 
titatively determined  §  by  diluting  the  oil  with  an  equal 
volume  of  benzole  and  whirling  it  in  a  centrifuge  until 
the  separated  layer  of  water  does  not  appear  to  increase 
in  volume.  The  benzole  should  have  been  thoroughly 
shaken  with  water  and  centrifuged  at  the  same  tem- 


*  J.  Ind.  and  Eng.  Chem.,  2,  171  (1910). 

f  J.  Am.  Chem.  Soc.,  26,  341  (1904). 

t  Holley  and  Ladd,  Mixed  Paints,  Color  Pigments  and  Varnishes,  p.  36. 

§  Charitschkoff,  Chem,  Zeit.,  33,  93  (1906). 


FUEL  ANALYSIS— HEATING  VALUE.  8 1 

perature  for  the  same  length  of  time  in  order  to  saturate 
the  benzole  with  water. 

Flash  and  Fire  Test. — Determined  by  heating  the 
oil  hi  the  covered  New  York  tester  or  lubricating  oil  tester 
according  to  Gill,  "  Short  Handbook  of  Oil  Analysis," 
Chapters  I  and  II. 

The  analysis  of  gaseous  fuels  has  already  been  de- 
scribed in  Chapter  V. 

DETERMINATION   OF   CALORIFIC   POWER   OF   SOLID 
AND    LIQUID    FUEL 

a.  Direct  Methods. 

Many  forms  of  apparatus  have  been  proposed 
for  this  purpose;  few,  however,  with  the  exception  of 
those  employing  Berthelot's  principle — of  burning  the 
substance  under  a  high  pressure  of  oxygen — have  yielded 
satisfactory  results.  The  apparatus  of  William  Thom- 
son,* and  also  that  of  Barrus,  in  which  the  coal  is  burnt 
in  a  bell-jar  of  oxygen  under  water,  while  usually  yield- 
ing results  within  3  per  cent  of  the  calculated  value,  yet 
they  may  vary  as  much  as  8  per  cent  from  that  value,  f 
Unless  a  crucible  lined  with  magnesia  be  used,  or  the 
sample  mixed  with  bituminous  coal,  it  is  inapplicable 
to  certain  semi-bituminous  and  anthracite  coals,  as  the 
ash  formed  over  the  surface  prevents  the  combustion  of 
the  coal  beneath  it. 

Fischer's  calorimeter  f  is  similar  in  principle,  but  is 
claimed  to  give  very  good  results.  § 

*  Thomson,  Jour.  Soc.  Chemical  Industry,  5,  581. 

t  Ibid.,  8,  5 25- 

}  Zeit.  f.  angewandte  Chemie,  12,  351. 

§  Bunte,  Jour.  f.  Gasbeleuchtung  und  Wasserversorgung,  34,  21,  41. 


82  GAS  AND  FUEL  ANALYSIS. 

Lewis  Thompson's  calorimeter,  in  which  the  coal  is 
burnt  in  a  bell-jar  by  the  aid  of  oxygen  furnished  by 
the  decomposition  of  potassium  chlorate  or  nitrate,  is 
open  to  several  objections,  the  chief  of  which  are: 
i.  The  evolution  of  heat  due  to  the  decomposition  of  the 
oxidizing  substance  used.  2.  Loss  of  heat  due  to  mois- 
ture carried  off  by  the  gases  in  bubbling  through  the 
water.  The  results  which  it  gives  must  be  increased  by 
15  per  cent.* 

Hempel's  apparatus  f  makes  use  of  the  Berthelot 
principle:  the  coal  must  be  compressed  into  a  cylinder 
for  combustion — a  process  to  which  every  coal  is  not 
adapted — only  applicable  to  certain  varieties  of  bitumin- 
ous and  brown  coal.  The  mixture  with  the  coal  of  any 
cementing  or  inflammable  substance  to  form  these  cylin- 
ders carries  with  it  the  necessity  of  accurately  determining 
its  calorific  power  beforehand. 

Numerous  other  workers  have  experimented  with  the 
bomb  calorimeter,  Mahler,  At  water,  Kroecker,  Williams, 
Norton,  Parr  and  Emerson;  as  the  last  apparatus  is  now 
in  common  use  it  will  be  described  here.J 

Details  of  Emerson  Apparatus. 

Bomb. — The  bomb  is  made  of  steel,  consisting  of  two 
cups  joined  by  means  of  a  heavy  steel  nut.  The  cups 
are  machined  at  their  contact  faces  with  a  tongue  and 
groove,  the  joint  being  made  tight  by  means  of  a  lead 
gasket  inserted  in  the  groove.  The  lining  is  of  sheet 


*  Scheurer-Kestner,  J.  Soc.  Chem.  Industry,  7,  869  (i 

f  Hempel,  Gasanalytische  Methoden,  p.  347. 

%  From  the  circular  accompanying  the  apparatus. 


FUEL  ANALYSIS— HEATING  VALUE.  83 

metal,  usually  pure  nickel,  although  gold  and  platinum 
are  sometimes  used,  spun  to  fit  the  interior.     The  bomb  is 

S 


EMERSON-FUEL-CALORIMETER 
FIG.  1 6, 


made  up  tight  with  a  milled  wrench  or  spanner.  The 
pan  holding  the  combustible  is  of  platinum  or  nickel, 
and  the  supporting  wire  of  nickel.  The  fuse  wire  should 


84  GAS  AND  FUEL  ANALYSIS. 

be  platinum  in  general  fuel  testing.  In  standardizing 
the  calorimeter  by  means  of  cane  sugar,  benzoic  acid, 
etc.,  it  is  necessary  to  use  iron  fuse  wire. 

Calorimeter.— The  jacket  is  either  a  double-walled 
copper  tank,  between  the  walls  of  which  water  is  inserted, 
or  a  vacuum- walled  cup.  The  calorimeter  bucket  proper, 
inside  this,  is  made  as  light  as  possible  of  sheet  brass. 

Stirring  Device.  S,  Fig.  16. — This  consists  of  a  paddle- 
wheel  shaft  enclosed  in  a  vertical  tube  to  facilitate  its 
action  in  circulating  the  water.  The  stirrer  shaft  is 
driven  by  a  belt  from  a  small  motor  at  the  other  end  of  the 
stirrer  bracket.  The  motor  is  mounted  on  a  sliding  plate 
which  permits  of  varying  the  tension  on  the  belt.  This 
varying  tension  serves  to  regulate  the  speed  of  the  paddle 
shaft  by  thus  varying  the  speed  of  the  motor.  The 
stirrer  is  mounted  on  a  post  on  the  calorimeter  jacket,  as 
is  the  thermometer  holder. 

The  motor  is  driven  from  a  i  lo-volt  circuit,  and  should 
be  placed  in  series  with  a  6o-watt  lamp.  If  so  desired,  a 
motor  driven  by  a  battery  can  be  specified  in  ordering 
the  apparatus.  The  battery  motor  is  driven  by  a  six- 
volt  storage  battery.  These  motors  designed  for  the  no- 
volt  power  circuit  may  be  driven  on  other  voltage  pro- 
vided that  a  proper  resistance  be  placed  in  series  so  that 
the  current  in  the  circuit  is  one-half  ampere.  The  motor 
may  be  driven  by  either  direct  or  a  6o-cycle  alternating 
current. 

Oxygen  Piping.  Fig.  17. — The  piping  for  the  insertion 
of  oxygen  under  pressure  is  made  especially  strong  and 
durable.  The  piping  of  small  internal  bore  is  made  of 
heavy  brass.  The  system  is  fitted  with  a  hand  nipple  at 
one  end  to  make  the  connection  with  the  bomb,  and  the 


FUEL  ANALYSIS— HEATING  VALUE.  85 

other  end  has  a  special  fitting  to  grasp  the  oxygen  supply 
tank.*  Commercially  pure  oxygen,  free  from  all  traces 
of  combustible  gases,  should  be  used. 

Iron  Plate  Holder. — The  plate  holder  or  vise  is  to  be 
used  when  tightening  the  nut  of  the  bomb  with  the  spanner. 

Swivel  Table. — The  table  with  the  rotating  top  is  to 
hold  the  bomb  when  the  same  is  connected  to  the  oxygen 


FIG.  17. 

piping.     (See  Fig.  17.)     This  swivel  table  is  not  included 
with  the  double  outlet  bomb. 

Spanner. — The  spanner  or  wrench  is  a  forging  with 
30-inch  handle  and  is  used  to  make  bomb  up  with  gas- 
tight  joint. 

*  Furnished  by  the  S.  S.  White  Dental  Manufacturing  Company. 
Piping  to  fit  other  tanks  can  be  furnished  to  order. 


86  GAS  AND  FUEL  ANALYSIS. 

Thermometer  Telescope. — Hand  telescope  to  enable 
operator  to  read  thermometer  to  roVo  or  T^Vo  of  a 
degree. 

Determination  of  Heat  of  Combustion  of  Fuels 
and  Other  Combustibles. 

COAL. 

Manipulation. — Place  the  lower  half  of  the  bomb  in 
the  iron  plate  holder  and  adjust  the  fuel  pan  support -in 
proper  position.  This  support  is  held  by  a  taper  pin 
which  fits  into  the  inner  end  of  the  insulation  plug,  which 
plug  is  at  the  side  of  the  lower  cup  of  the  bomb.  The 
taper  pin  holding  the  fuel  pan  support  should  be  entered 
firmly  into  the  porcelain  plug  in  order  that  the  support 
will  not  permit  of  tipping,  which  would  likely  result  in 
the  upsetting  of  the  charge  of  fuel  at  the  time  of  ignition. 
To  enter  the  taper  pin  in  place,  use  the  small  steel  spanner 
which  fits  into  the  recess  of  the  taper  pin.  This  spanner 
will  also  be  found  suitable  for  removing  the  taper  pin 
from  the  plug.  Care  should  be  taken  on  the  interior  of  the 
bomb  that  the  linings  do  not  touch  the  metal  part  of  the  insu- 
lation taper  pin  which  holds  the  fuel  pan  support. 

The  fuse  wire  is  connected  to  the  binding  post  on  the 
fuel  pan  support  and  extends  across  the  bomb  to  the  bind- 
ing post  at  the  opposite  side  of  the  bomb,  sufficient  length 
being  allowed  that  the  wire  will  dip  down  sufficiently  to 
be  in  contact  with  the  fuel  which  is  afterwards  placed  in 
the  pan.  Care  must  be  taken  that  the  wire  does  not  touch 
the  fuel  pan. 

The  fuel  used  is  sampled,  crushed,  and  powdered 
according  to  directions  given  on  page  72. 


FUEL  ANALYSIS— HEATING  VALUE.  87 

Fill  a  test-tube  or  convenient  weighing  vial  with  the 
prepared  sample  and  weigh  it  accurately  to  one-tenth  of  a 
milligram.  Pour  from  this  into  the  pan  in  the  bomb  until 
the  pan  is  approximately  half  full.  Weigh  the  vial  again 
and  the  difference  of  the  above  weighings  gives  us  the  net 
quantity  of  fuel  in  the  bomb.  This  weight  should  be 
greater  than  five-tenths  of  a  gram,  and  not  more  than  one 
and  two-tenths  grams.  For  hard  coal  the  maximum 
charge  should  be  not  greater  than  one  gram.  Hard  coal 
should  not  be  as  finely  divided  as  soft  coal.  (Through  an 
8D-mesh  sieve  is  sufficient.) 

The  upper  half  of  the  bomb  is  placed  in  position  and 
the  nut  screwed  down  as  far  as  may  be  by  hand,  care 
being  taken  not  to  cross  the  threads.  The  shoulder  on  the 
upper  half  of  the  bomb  over  which  the  nut  makes  bearing 
contact  should  be  thoroughly  lubricated  with  oil.  Extreme 
care  should  be  taken  that  no  oil  or  grease  is  deposited  on 
the  lead  gasket,  as  the  bomb,  when  working  properly, 
closes  without  the  upper  half  turning  on  the  gasket  on 
account  of  the  contact  friction  of  the  nut.  Any  oil  on 
the  lead  gasket  would  tend  to  hinder  the  proper  action  in 
this  respect. 

The  large  wrench  is  used  to  make  the  joint  tight,  and 
operator  should  apply  the  same  very  nearly  to  his  full 
strength.  (If  the  thread  of  the  large  nut  is  kept  free  from 
dirt,  it  will  turn  into  place  freely  by  hand.) 

The  bomb  is  now  ready  to  be  filled  with  oxygen,  and 
this  is  accomplished  by  means  of  the  spindle  valve  at  the 
top  of  the  bomb.  The  nipple  is  coupled  to  the  oxygen 
piping  by  means  of  the  attached  hand  union,  the  bomb 
resting  on  the  swivel  table.  (The  oxygen  piping  should  be 
properly  located  and  screwed  fast  to  the  bench.)  The 


88  GAS  AND  FUEL  ANALYSIS. 

screw  holes  in  the  feet  of  the  sv/ivel  table  are  left  large  and 
are  made  for  round-head  screws  so  as  to  allow  for  adjust- 
ment relative  to  the  oxygen  piping.  Both  should  be  fixed 
in  position.  In  handling  the  bomb,  care  should  be  taken 
not  to  tip  or  jar  it,  as  fuel  may  be  thrown  from  the  pan. 

The  spindle  valve  on  the  bomb  need  only  be  opened 
one  turn,  and  then  the  valve  on  the  oxygen  supply  cylinder 
is  very  cautiously  opened.  The  pressure  gauge  should  be 
carefully  watched  and  the  cylinder  valve  so  regulated 
that  the  pressure  in  the  system  shall  rise  very  gradually. 
When  the  pressure  reaches  300  pounds  per  square  inch, 
the  cylinder  valve  is  closed,  and  then  the  spindle  valve 
on  the  bomb  immediately  after. 

The  bomb  should  be  immersed  in  water  immediately 
to  detect  any  possible  leakages.  (Preferably  a  glass  jar, 
as  slight  leaks  are  detected  by  looking  from  all  sides.) 

The  bomb  is  now  ready  for  the  calorimeter,  which  is 
prepared  as  follows : 

Nineteen  hundred  grams  of  water  are  placed  in  the 
calorimeter  can  at  a  temperature  about  i-J-0  below  the 
jacket  temperature  (which  temperature  should  be  in 
the  proximity  of  the  room  temperature.)  The  bomb  is 
then  placed  in  the  can;  care  should  be  taken  that  the 
outer  surface  of  this  can  is  thoroughly  dry;  the  stirrer 
and  thermometer  are  lowered  into  position  as  indicated 
by  the  illustration.  The  thermometer  is  immersed  about 
3  inches  in  the  water  and  the  thermometer  bulb  should 
be  at  least  \  inch  from  the  bomb.  Care  should  be  taken 
that  the  bomb  does  not  touch  the  sides  of  the  can  or  that 
the  stirrer  does  not  touch  the  bomb. 

Ignition  Wiring. — One  terminal  of  the  electric  circuit 
for  igniting  the  charge  is  connected  to  the  bomb  by  means 


FUEL  ANALYSIS— HEATING  VALUE.  89 

of  the  taper  binding  post  which  fits  into  the  spindle  at 
the  top,  and  the  other  is  connected  to  the  outer  end  of 
the  insulation  plug  on  the  lower  cup  01  the  bomb.  A 
short  length  of  insulated  wire,  which  is  connected  to  a 
small  taper  pin  fitting  into  the  outer  end  of  the  insulation 
plug,  is  included  with  the  apparatus.  The  other  end  of 
this  piece  of  insulated  wire  is  fitted  with  a  connector  for 
one  terminal  from  the  switchboard.  This  last-mentioned 
taper  pin  is  fitted  into  the  plug  before  the  bomb  is  lowered 
into  the  calorimeter  bucket.  Two  ico-watt  lamps  in 
parallel  are  placed  in  series  with  the  fuse  wire  when  no- 
volt  circuit  is  used  for  firing. 

The  Run. — The  stirrer  is  started,  and  allowed  to  run 
three  or  four  minutes  to  equalize  the  temperature  through- 
out the  calorimeter.* 

Readings  of  the  thermometer  are  taken  for  five  minutes 
(reading  to  the  yoVo  or  y^o  of  a  degree  every  minute), 
at  the  end  of  which  time  the  switch  is  turned  on  for  an 
instant  only,  which  will  be  found  sufficient  to  fire  the 
charge.  In  course  of  a  few  seconds  the  temperature  begins 
to  rise  rapidly  and  readings  are  taken  every  half  minute 
from  the  time  of  firing.  After  a  maximum  temperature 
is  reached  and  the  rate  of  change  of  temperature  is  evi- 


*  If  the  stirrer  gives  trouble  by  refusing  to  run  at  sufficient  speed  or 
by  stopping  completely,  the  difficulty  is  usually  due  to  the  accumulation 
of  oil  on  the  commutator  The  operator  can  readily  remove  the  oil 
with  chamois  cloth  and  by  using  care,  this  removal  of  the  oil  from  the 
commutator  can  be  accomplished  when  the  stirrer  is  running.  Draw  the 
chamois  tightly  over  the  forefinger  and  press  gently  on  the  surface  of  the 
commutator,  taking  care  not  to  injure  the  brushes. 

If  the  stirrer  runs  at  too  high  speed  causing  the  water  in  the  calorimeter 
can  to  be  thrown  about,  a  rheostat  placed  in  series  with  the  motor  will 
serve  to  regulate  and  modify  the  speed. 


90  GAS  AND  FUEL  ANALYSIS. 

dently  due  only  to  the  radiation  to  or  from  the  calorimeter, 
the  readings  are  continued  for  an  additional  five  minutes, 
reading  every  minute.  These  readings  before  the  firing 
and  after  the  maximum  temperatures  are  necessary  in  the 
computation  of  the  cooling  correction.  The  time  elapsed 
from  the  time  of  firing  to  the  maximum  temperature  should 
be  in  no  case  more  than  six  minutes. 

When  through  with  run,  replace  bomb  in  the  holder  and 
allow  the  products  of  combustion  from  within  to  escape 
through  the  valve  at  the  top  of  the  bomb.  Unscrew  the 
large  nut  and  clean  the  interior  of  the  bomb.  The  inside 
of  the  nut  should  be  kept  oiled ;  and  also  the  threaded  part 
at  the  top  of  the  lower  cup. 

Immediately  after  each  run  the  inside  of  the  bomb  should 
be  dried  out  with  a  cloth.  The  lining  of  the  lower  cup 
is  removed  by  withdrawing  the  fuse- wire  binding  post 
which  is  held  in  place  with  a  taper  fit  and  is  easily  removed. 
The  lining  to  the  upper  cup  is  held  in  place  by  the  small 
screw  at  the  top  which  holds  the  deflector. 

After  each  day's  run  the  linings  should  be  removed  and 
the  inner  surface  of  the  bomb  under  the  linings  should  be 
coated  slightly  with  oil.  (This  oil  must  positively  be 
removed  when  the  bomb  is  in  operation.) 

The  pan  may  be  cleaned  by  boiling  in  dilute  hydro- 
chloric acid.  Any  further  slag  clinging  to  the  pan  may 
be  fused  with  sodium  carbonate.  The  fused  mass  dis- 
solves in  hot  water. 

Computation.— The  data  obtained  during  the  run  are 
used  as  follows: 

To  the  temperature  in  the  calorimeter  at  firing  and  the 
maximum  temperature  is  applied  the  correction  for  the 
errors  on  the  thermometer,  which  are  obtained  from  the 


FUEL  ANALYSIS— HEATING  VALUE.  91 

table  of  corrections  supplied  with  the  thermometer  when 
it  is  standardized  at  the  Bureau  of  Standards.  The  dif- 
ference between  these  corrected  temperatures  at  maxi- 
mum and  firing  gives  the  true  rise  of  temperature  in  the 
calorimeter,  and  to  which  must  be  added  a  cooling  cor- 
rection, which  is  computed  as  follows: 

The  change  in  temperature  during  the  preliminary 
five  minutes  of  reading,  divided  by  the  time  (five  minutes), 
gives  the  rate  of  change  of  temperature  per  minute,  due 
to  radiation  to  or  from  the  calorimeter,  and  also  any 
heating  due  to  stirring,  etc.  Call  this  factor  Riy  and  in 
like  manner  the  readings  taken  after  the  maximum  tem- 
perature give  R2.  The  rates  of  change  of  temperature 
give  the  existing  conditions  in  the  calorimeter  at  the 
start  and  at  the  finish  of  the  run.  The  radiation  to  and 
from  the  calorimeter  when  the  same  is  at  room  tempera- 
ture is  o.  Therefore: 

7?    LQ 

— X  (time  from  firing  temperature  to  room  temperature) 

expresses  the  exchange  of  heat  to  and  from  the  calorimeter 
in  that  part  of  the  run  from  firing  temperature  to  room 
temperature.  In  the  same  manner  the  expression 

—  X  (time  from  room  temp,  to  maximum  temp.) 

gives  a  close  approximation  of  the  exchange  of  heat  to 
and  from  the  calorimeter  during  the  latter  part  of  the 
run. 

In  the  first  factor  above  mentioned,  as  the  time  from 
firing  temperature  to  room  temperature  is  invariably 


92  GAS  AND  FUEL  ANALYSIS 

close  to  one  minute,  the  expression  for  cooling  can  be 

written  as  follows: 

j\     r/?  ~i  * 

—  +    —  X  (time  from  room  temp,  to  maximum  temp.)   . 

This  latter  quantity  is  either  added  to  or  subtracted 
from  the  above  corrected  rise  in  temperature,  accordingly 
as  the  balance  of  heat  radiation  is  to  the  surroundings  or 
from  the  surroundings.  This  is  at  once  determined  from 
an  inspection  of  the  data.  This  rise,  of  temperature,  cor- 
rected for  thermometer  calibration  errors,  and  with  the 
cooling  correction  applied,  is  divided  by  the  weight  of 
fuel  used,  thus  giving  directly  the  rise  in  temperature  per 
gram  of  fuel. 

This  rise  per  gram,  times  the  weight  of  water,  plus 
"  water  equivalent "  (see  "  standardization,")  will  give 
immediately  the  calories  per  gram  of  fuel,  which  is  the 
result  to  be  obtained.  The  result  in  calories  per  gram 
of  fuel  multiplied  by  the  factor  1.8  gives  B.T.U.  per 
pound  of  fuel. 

HEAVY  OILS,  COKE,  HARD  COAL,  ETC. 

The  determination  of  the  heat  of  combustion  of  heavy 
oils  such  as  crude  petroleum,  and  also  of  coke  and  ex- 
tremely hard  coals,  is  best  made  by  burning  them  mixed 

*  If  due  to  unusual  atmospheric  temperatures  the  run  is  made  with 
temperatures  all  below  or  temperatures  all  above  room  temperature, 

r  /?  i  /?  n 

then  the  expression  I  -    X  (time  from  firing  temperature  to  maxi- 

mum temperature)  gives  a  close  approximation  for  the  cooling  correc- 
tion. For  an  even  closer  approximation  of  the  radiation  correction,  the 
Regnault-Pfaundler  formula  is  recommended. 


FUEL  ANALYSIS— HEATING  VALUE.  93 

with  a  ready-burning  combustible,  such  as  a  high-grade 
bituminous  coal.  This  auxiliary  combustible  facilitates 
the  complete  combustion  of  the  whole  mixture  in  case  of 
coke  and  hard  coal,  and  with  the  heavy  oil  it  acts  as  a 
holder  and  prevents  rapid  evaporation  of  the  oil. 

A  known  weight  of  the  auxiliary  combustible  should  be 
placed  at  the  bottom  of  the  pan  and  the  coke,  coal  or  oil 
sprinkled  over  it.  The  auxiliary  combustible  should  be 
dried  and  carefully  standardized  as  to  its  rise  in  tempera- 
ture per  gram  in  the  calorimeter  when  the  same  is  com- 
pletely burned. 

Weighing  of  Fuel  Oils. — In  the  handling  of  fuel  oil, 
the  most  suitable  method  of  preventing  evaporation  in 
weighing  the  sample  is  to  hold  it  in  a  small  weighing  bottle 
with  a  dropper  arranged  in  the  stopper  for  the  purpose  of 
conveying  the  liquid  fuel  to  the  sample  of  standard  com- 
bustible in  the  fuel  pan;  and  after  a  few  drops  have  been 
placed  here,  the  stopper  is  put  again  in  the  weighing 
bottle  and  the  whole  is  reweighed.  The  difference 
between  this  weight  and  the  weight  previous  to  the  taking 
out  of  the  sample  gives  the  net  weight  of  fuel  oil  in  the 
bomb.  The  upper  half  of  the  bomb  should  be  imme- 
diately placed  in  position  to  prevent  as  much  as  possible 
the  vaporization  of  the  sample. 

LIGHT  FUEL  OILS,  GASOLINE,  ALCOHOL,  ETC. 

Because  of  the  rapid  evaporation  of  the  lighter  fuel  oils 
it  is  not  advisable  to  pour  it  directly  into  the  fuel  pan. 
Small  gelatine  capsules  can  be  obtained  which  may  be 
filled  with  ignited  asbestos  into  which  the  light  oils  may 
be  poured  and  absorbed  by  the  asbestos.  The  filled 


94  GAS  AND  FUEL  ANALYSIS, 

capsule  is  sealed,  placed  in  the  fuel  pan  and  burned  in 
the  usual  manner,  using  iron  wire  for  ignition.  The  dry 
weight  of  the  capsule  and  asbestos  must  be  known  and 
after  filling  capsule  with  charge  and  sealing  it,  the  weight 
of  the  whole  is  taken.  Care  should  be  used  that  no  air 
bubbles  are  enclosed  with  the  charge  in  the  capsule,  as 
the  fuel  will  otherwise  ignite  with  explosive  violence. 

THERMOMETERS. 

The  accuracy  of  the  calorimeter  depends  largely  on  the 
accuracy  of  the  thermometer  used  in  connection  with  the 
same.  A  good  grade  calorimetric  thermometer,  gradu- 
ated in  rg-Q  or  -^  of  a  degree,  ranging  from  about  15°  to 
28°  C.,  is  a  desirable  type.  This  thermometer  should  have 
a  Bureau  of  Standards  calibration  certificate. 

A  Beckman  type  of  thermometer  with  Bureau  of  Stand- 
ards certificate  is  satisfactory. 

STANDARDIZATION   OF   CALORIMETER. 

In  the  measurement  of  the  heat  of  combustion  of  a  fuel 
or  a  combustible  in  a  bomb  calorimeter,  the  immersed 
parts  of  the  calorimeter  including  the  bomb,  can,  stirrer, 
etc.,  are  carried  through  the  same  rise  in  temperature  as 
the  water.  The  amount  of  heat  absorbed  by  these  im- 
mersed parts  for  one  degree  rise  in  temperature  is  known 
as  the  "  Water  Equivalent "  factor  of  the  apparatus. 

A  bomb  calorimeter  when  operated  properly  will  give 
the  true  heat  value  of  a  given  combustible  if  as  a  water 
equivalent  factor  we  use  that  obtained  from  the  weights 
and  specific  heats  of  the  immersed  parts,  i.e.,  the  sum  of 
the  products  of  the  weight  of  each  part  times  its  specific 


FUEL  ANALYSIS— HEATING  VALUE.  95 

heat.  The  work  of  such  physicists  as  Berthelot  and 
Mahler  has  conclusively  proven  that  this  above  method  is 
correct.  It  is  sometimes  desirable  to  check  this  value  by 
burning  a  combustible  of  known  calorific  value.  Extreme 
care  should  be  taken  that  such  standardizing  substances 
should  be  of  100  per  cent  purity  and  absolutely  free  from 
chemically  or  physically  combined  water. 

The  value  of  such  a  standard  substance  in  calories  per 
gram  is  divided  by  the  rise  in  temperature  hi  the  calor- 
imeter per  gram  of  sample,  and  the  result  is  the  water 
plus  the  water  equivalent  of  the  apparatus.  The  water 
being  known,  the  water  equivalent  is  thus  determined. 

With  a  combustible  of  absolute  purity  this  determina- 
tion will  check  the  value  of  the  water  equivalent  as  figured 
from  the  weights  and  specific  heat  of  the  material  included 
in  the  immersed  parts  of  the  calorimeter. 

The  chemically  pure  cane  sugar,  benzoic  acid  and 
naphthaline  obtained  at  the  Bureau  of  Standards,  Wash- 
ington, D.  C.,  are  the  only  suitable  materials  to  be  used 
for  the  purpose  of  standardization  of  bomb  calorimeters. 
These  materials  are  prepared  by  the  Bureau  specifically 
for  laboratories  and  users  of  combustion  apparatus.  The 
sample  as  received  from  the  Bureau  is  in  a  finely  divided 
condition  suitable  to  be  used  for  the  work  of  standardiza- 
tion. With  naphthaline,  the  sample  should  be  briquetted 
or  fused  into  a  solid  mass. 

To  standardize  the  calorimeter  with  one  of  the  above 
materials,  the  bomb,  fuel  pan  and  fuse  wires  are  prepared 
in  the  same  manner  as  in  the  testing  of  a  fuel,  except  that 
the  fuse  wire  should  be  of  iron  instead  of  platinum.  The 
iron  wire  at  the  point  where  it  touches  the  combustible 
should  be  wound  in  a  narrow  helix.  The  pan  should  be 


96  GAS  AND  FUEL  ANALYSIS. 

about  three-quarters  filled  with  a  known  weight  of  the 
standard  substance  used,  the  iron  fuse  wire  resting  on  its 
surface.  One  or  two  flakes  of  chemically  pure  naphthaline 
should  be  sprinkled  on  the  coil  where  it  is  in  contact  with 
the  material  when  cane  sugar  is  used.  These  small  pieces 
of  naphthaline  act  as  an  igniter.  For  different  diameters 
of  iron  fuse  wire  it  will  be  necessary  to. change  somewhat 
the  resistance  placed  in  series  with  the  same.  With  wire 
about  three-  or  four-thousandths  of  an  inch  in  diameter, 
two  i oo- watt  lamps  should  be  placed  in  the  firing  circuit 
in  parallel  and  in  series  with  the  iron  fuse  wire.  Wires 
larger  than  this  latter  diameter  should  have  three  or  four 
lamps  in  parallel  according  to  the  size  of  the  same. 

In  making  a  run  the  weight  of  combustible  is  recorded, 
the  weight  of  the  naphthaline  used  as  an  igniter,  and  the 
weight  of  the  iron  fuse  wire  burned.  The  latter  quantity 
is  obtained  by  weighing  the  entire  piece  of  fuse  wire  orig- 
inally connected  in  the  bomb,  and  subtracting  from  that 
weight  of  the  unburned  ends  if  any  are  found  after  the  run. 
The  following  corrections  must  be  made  : 

1.  The  heat  generated  by  the  burning  of  the  small 
quantity  of  naphthaline  used  as  an  igniter. 

2.  The  heat  generated  by  the  burning  of  the  iron  fuse  wire. 

3.  The   heat  input    of  the  electrical   current  used  in 
bringing  the  fuse  wire  to  incandescence. 

4.  The  heat  of  formation  of  nitric  acid. 

With  reference  to  the  above: 

The  heat  of  combustion  of  naphthaline  is  9610  calories 
per  gram. 

The  heat  of  combustion  of  iron  wire  is  1600  calories 
per  gram. 


FUEL  ANALYSIS— HEATING  VALUE.  97 

The  correction  for  electrical  input  can  be  best  deter- 
mined by  a  blank  run  in  which  wire  of  the  same  diameter 
as  that  to  be  used  in  the  test  is  burned  in  the  bomb  without 
the  presence  of  a  charge  of  combustible.  This  blank  run 
is  made  with  the  temperature  in  the  calorimeter  bucket 
exactly  the  same  as  the  surrounding  conditions,  in  order 
that  a  cooling  correction  will  be  avoided.  When  the  tem- 
peratures within  and  without  the  calorimeter  are  exactly 
equalized,  the  current  is  turned  on  and  the  iron  wire 
ignited.  The  current  is  turned  on  for  an  exact  period 
of  time,  i.e.,  either  of  one  or  two  seconds'  duration.  This 
continuation  of  the  flow  of  current  should  be  exactly 
duplicated  when  the  standardization  run  is  being  made 
and  the  standard  combustible  is  being  burned.  From 
the  total  calories  developed  in  the  blank  run  should  be 
subtracted  the  heat  developed  due  to  the  burning  of  the 
known  weight  of  iron  wire.  The  remainder  gives  the 
amount  due  to  the  flow  of  current. 

In  supplying  the  correction  for  the  formation  of  nitric 
acid,  an  arbitrary  correction  of  about  ten  calories  is  satis- 
factory. 

These  above  corrections  are  all  subtractive  and  are  de- 
ducted from  the  results  as  obtained  from  the  calorimeter  test. 

The  mean  value  for  the  heat  of  combustion  of  cane  sugar 
is  3950  calories  per  gram.  The  heat  of  combustion  of 
benzoic  acid  is  6320  calories  per  gram. 

For  further  detailed  information  regarding  the  standard- 
ization of  bomb  calorimeters,  Circular  No.  n  of  the 
Bureau  of  Standards  is  recommended. 

The  water  equivalent  factor  of  the  Emerson  Fuel 
Calorimeter,  as  computed  from  the  immersed  parts  and 
their  specific  heats,  is  furnished  with  the  outfit. 


98  GAS  AND  FUEL  ANALYSIS. 

Specific  heat  of  steel  =  0.116;  of  nickel  =  0.109;  °f 
brass  =  0.094;  of  vulcanite  =  0.331;  of  copper  =  0.092  ; 
of  platinum  =  0.03  2. 

Heat  of  Combustion. 
SAMPLE  RUN. 

November  20,  1912. 

Sample  No.  1  28  (air  dried.)  Run  No.  2. 

Thermometer  used,  No.  2295. 

Weight  of  tube  and  coal  =  7.9379  Room  Temp.  =  22°  C. 

Weight  of  tube  and  coal  =  7.  071^ 

Weight  of  fuel  .8666  gram 

Weight  of  water  1900  grams 

READINGS  OF  THERMOMETER. 

Time  Temp. 

0  20.348 

1  20.352 

2  20.358 

3  20.362 

4  20.368 

5  20.376  Firing  Temp. 
30  21.000 


Temperature  at  firing  =  20.3  76+     (—.on)     =20.365 

Temperature  at  max.  =23.196+     (+.002)     =23.198 

Rise  in  temperature  corrected  for  errors  in  thermometer  =2.  833 

Rate  of  change  of  temperature  before  firing  =  0.0056=^1 

Rate  of  change  of  temperature  after  maximum  temperature  =  0.0088  =R2* 

(-.0056)  (+.0088) 

Total  cooling  corr.  =  —        -  •  X(i)+  --  -X(2.s)  =  .oo8  (additive) 

Total  corrected  rise  in  temperature  =2.841. 

Rise  per  gram  of  sample  =  3.  2  78 

The  water  equivalent  of  bomb,  calorimeter  can,  stirrer,  etc.  =490 

Gram  calories  per  gram  of  coal=  (19004-490)  X3-278  =  7834 

British  Thermal  Units  per  pound  of  coal  =7834X1.  8  =  14,100 

*  Rate  for  last  five  minutes. 


Time         Temp. 

Time 

Temp. 

6          22.600 

IO 

2.3-IQ4 

30      22.900 

II 

23.182 

7          23.100 

12 

23.174 

30      23.150 

13 

23.166 

8          23.194 

14 

23-158 

30     23.196  Max. 

Temp.    15 

23-150 

9          23.196 

30    23.194 

/CalibrationN 

\  Correction  / 

FUEL  ANALYSIS— HEATING  VALUE.  99 

Berthier's  Method. — Another  method  of  direct  deter- 
mination was  proposed  by  Berthier  in  1835.*  It  uses 
as  a  measure  of  the  heating  value  the  amount  of  lead 
which  a  fuel  would  reduce  from  the  oxide;  in  other 
words  it  is  proportional  to  the  amount  of  oxygen  ab- 
sorbed. 

The  method  is  as  follows  | :  Mix  one  gram  of  the 
finely  powdered  dry  coal  with  60  grams  of  oxide  of  lead 
(litharge)  and  10  grams  of  ground  glass.  This  mixing 
can  be  done  with  a  palette-knife  on  a  sheet  of  glazed 
paper;  the  mixture  is  transferred  to  a  fire-clay  crucible 
(Battersea  C  size),  covered  with  salt,  the  crucible  covered 
and  heated  to  redness  in  a  hot  gas-furnace — or  the  hottest 
part  of  the  boiler-furnace — for  15-20  minutes.  After 
cooling,  the  crucible  is  broken  and  the  lead  button  care- 
fully cleaned  and  weighed.  Multiply  the  weight  of  the 
lead  button  obtained  by  268.3  calories  (or  483  B.  T.  U.) 
and  divide  the  product  by  the  weight  of  coal  taken.  The 
result  is  the  number  of  calories  per  gram  or  B.  T.  U.  per 
pound.  One  gram  of  lead  is  theoretically  equivalent  to 
234  calories  (C) ;  owing  to  the  hydrogen  present  this  factor 
gives  results  about  2  per  cent  too  low.  The  results  ob- 
tained by  the  author  using  "  horn-pan  "  scales  in  one  case 
by  this  method  were  within  2.8  per  cent  of  those  yielded 
by  the  bomb  calorimeter,  which  are  as  close  as  those 
obtained  by  any  calorimeter  save  Parr's.  The  method 
would  seem  worthy  of  more  attention  than  it  has  re- 
ceived. 

*  Dingler's  Polytechnisches  Journal,  58,  391. 

t  Noyes,  McTaggart  and  Graver,  J.  Am.  Chem.  Soc.,  17,  847  (1895). 


loo  GAS  AND  FUEL  ANALYSIS. 

b.  Determination  of  Heating  Value  by  Calculation. 

The  method  of  determination  of  the  heating  value  first 
described,  though  exact,  has  the  disadvantages  that  the 
apparatus  is  costly  and  the  compressed  oxygen  is  not 
easily  obtained.  To  obviate  these,  it  has  been  sought  to 
obtain  the  heating  value  by  calculation  from  the  chem- 
ical analysis,  the  heating  value  of  the  constituents  being 
known.  This  has  the  disadvantage  that  we  have  no 
absolute  knowledge — nay,  not  even  an  approximate  idea — 
as  to  how  the  carbon,  hydrogen,  water,  and  sulphur  exist 
in  the  coal,  so  that  any  formula  must  of  necessity  be  quite 
removed  from  the  truth.  Dulong  was  the  first  to  propose 
the  method  by  calculations,  and  his  formula  as  modified 
by  Bunte  *  is 

SoSoc  +  28800 ( h  --  )  +  25005  -6oow 


100 

c,  h,  o,  s  and  w  representing  the  percentages  of  carbon, 
hydrogen,  oxygen,  sulphur  and  water  in  the  coal.  It  gives 
results  varying  from  +2.8  to  -3.7  per  cent;  it  would 
scarcely  seem  that  the  sulphur  would  be  worth  consider- 
ing unless  high,  i  per  cent  affecting  the  result  but  0.3 
per  cent.  The  hydrogen  is  considered  as  burned  to 
aqueous  vapor. 

The  results  obtained  by  these  formulae  for  anthracite 
coal  are  as  a  rule  considerably  too  low. 

The  heating  value  can  also  be  determined  from  the 
proximate  analysis — the  percentage  of  fixed  carbon  and 

*  Jour,  fur  Gasbeleuchtung,  34,  21-26  and  41-47. 


FUEL  ANALYSIS— tiEATING  VALUE. 


101 


volatile  matter;  this  has  been  well  shown  by  Maujer.* 
The  chart,  Fig.  18,  was  constructed  from  over  300 
analyses  of  representative  coal  made  by  the  Bureau  of 
Mines;  the  curve  is  most  accurate  for  coals  having  from 
64-90  per  cent  of  fixed  carbon  in  the  combustible  matter; 
where  this  is  less  than  64  per  cent  the  error  may  be  as 
much  as  7  per  cent.  To  determine  the  heating  value  of 


15,700  r- 

15,600  - 
15  500  — 

\ 

i=2 

!:s; 

^ 

15,400    - 

-     - 

.  ..  ^ 

15,300  - 
a,  15  200  - 

s-:::: 

|   15,100- 

r 

£  14,900  - 
£   14,800- 

::Z 

.  x  _  _  . 

«  14,700  - 
a  14,600  - 

/- 

!JE:i 

**                  B-/VA 

) 

14,400  - 

/ 

14,300 
14,200  - 

/ 

/ 

/ww» 

14,000^ 

55 

60             65 

70            75            80            85             90            95            100 
Per  Cent 

FIG.   1 8. — CHART  FOR  DETERMINING  HEAT  VALUE  OF  COMBUSTIBLE 
WITH  DIFFERENT  PERCENTAGES  OF  FIXED  CARBON. 

the  coal  from  the  chart,  the  percentage  of  fixed  carbon  is 
divided  by  the  sum  of  the  fixed  carbon  and  of  the  volatile 
combustible  matter  and  multiplied  by  100;  this  gives  the 
percentage  of  fixed  carbon  in  the  combustible  matter.  Let 
us  suppose  a  coal  of  this  composition;  moisture,  5.12, 

*  Power,  37,  836  (1913),  also  in  "Fuel  Economy  and  COz  Recorders," 
(1916),  pp.  45-47.     A  similar  curve  is  given  by  Kowalke,  Power,  35,  559 

(1912). 


102  GAS  AND  FUEL  ANALYSIS. 

volatile  combustible  matter  27.25,  fixed  carbon  53.38, 
and  ash  14.25  per  cent.  The  sum  of  the  volatile  matter 
and  fixed  carbon  is  (27.25  +  53.38)  =  80.63  divided  into  the 

fixed  carbon       j:    X 100  =  66.2  per  cent. 

That  is,  there  are  66.2  per  cent  fixed  carbon  in  the  total 
combustible  matter;  using  this  as  an  abscissa  (horizontal 
distance),  in  Fig.  18  we  find  15,400  B.  T.  U.  as  the 
corresponding  ordinate;  this  is  the  heating  value  of  the 
combustible  matter  in  the  coal;  since  by  the  above  cal- 
culation but  80.63  Per  cent  °f  tne  coal  is  combustible, 
the  heating  value  of  the  coal  is  80.63X15,400  or  12,420 
B.  T.  U. 

CALORIFIC  POWER   OF   GASEOUS   FUEL. 

a.  Direct  Determination. 

Perhaps  the  best  apparatus  for  the  determination  of 
the  heating  value  of  gases  is  the  Junkers  calorimeter, 
Figs,,  19  and  20.  The  following  description  is  taken 
from  an  article  by  Kiihne  in  the  Journal  of  the  Society 
of  Chemical  Industry,  vol.  14,  p.  631.*  As  will  be 
seen  from  Fig.  19,  this  consists  of  a  combustion-chamber, 
28,  surrounded  by  a  water-jacket,  15  and  16,  this  being 
traversed  by  a  great  many  tubes.  To  prevent  loss  by 
radiation  this  water-jacket  is  surrounded  by  a  closed 
annular  air-space,  13,  in  which  the  air  cannot  circulate. 
The  whole  apparatus  is  constructed  of  copper  as  thin  as 
is  compatible  with  strength.  The  water  enters  the  jacket 

*  See  also  Industrial  Gas  Calorimetry,  Tech.  Paper  No.  36,  Bur. 
Standards;  Standard  Methods  of  Gas  Testing,  Circular  No.  48,  Bur. 
Standards. 


FUEL  ANALYSIS— HEATING  VALUE. 


103 


at  i,  passes  down  through  3,  6,  and  7,  and  leaves  it  at  21, 
while  the  hot  combustion-gases  enter  at  30  and  pass 
down,  leaving  at  31.  There  is  therefore  not  only  a  very 


FIG.  19. — JUNKERS  GAS-CALORIMETER  (SECTION). 

large  surface  of  thin  copper  between  the  gases  and  the 
water,  but  the  two  move  in  opposite  directions,  during 
which  process  all  the  heat  generated  by  the  flame  is 
transferred  to  the  water,  and  the  waste  gases  leave  the 
apparatus  approximately  at  atmospheric  temperature. 
The  gas  to  be  burned  is  first  passed  through  a  meter, 


104  GAS  AND  FUEL  ANALYSIS. 

Fig.  20,  and  then,  to  insure  constant  pressure,  through 
a  pressure  regulator.  The  source  of  heat  in  relation  to 
the  unit  of  heat  is  thus  rendered  stationary  ;  and  in 


FIG.  20. — JUNKERS  GAS-CALORIMETER. 

order  to  make  the  absorbing  quantity  of  heat  also 
stationary,  two  overflows  are  provided  at  the  calo- 
rimeter, making  the  head  of  water  and  overflow  con- 
stant. The  temperatures  of  the  water  entering  and 
leaving  the  apparatus  can  be  read  by  12  and  43;  as 
shown  before,  the  quantities  of  heat  and  water  passed 


FUEL  ANALYSIS— HEATING  VALUE.  105 

through  the  apparatus  are  constant.  As  soon  as  the 
flame  is  lighted,  43  will  rise  to  a  certain  point  and  will 
remain  nearly  constant. 

Manipulation. — The  calorimeter  is  placed  as  shown 
in  Fig.  20,  so  that  one  operator  can  simultaneously 
observe  the  two  thermometers  of  the  entering  and 
escaping  water,  the  index  of  the  gas-meter,  and  the 
measuring-glasses. 

No  draft  of  air  must  be  permitted  to  strike  the  ex- 
haust of  the  spent  gas. 

The  water-supply  tube  w  is  connected  with  the 
nipple  a  in  the  centre  of  the  upper  container;  the 
other  nipple,  b,  is  provided  with  a  waste-tube  to  carry 
away  the  overflow,  which  latter  must  be  kept  running 
while  the  readings  are  taken. 

The  nipple  c  through  which  the  heated  water  leaves 
the  calorimeter  is  connected  by  a  rubber  tube  with 
the  large  graduate,  d  empties  the  condensed  water 
into  the  small  graduate. 

The  thermometers  being  held  in  position  by  rubber 
stoppers  and  the  water  turned  on  by  e  until  it  dis- 
charges at  c,  no  water  must  issue  from  d  or  from  39, 
Fig.  19,  as  this  would  indicate  a  leak  in  the  calorim- 
eter. 

The  cock  e  is  now  set  to  allow  about  two  liters  of 
water  to  pass  in  a  minute  and  a  half,  and  the  gas 
issuing  from  the  burner  ignited.  Sufficient  time  is 
allowed  until  the  temperature  of  the  inlet-water 
becomes  constant  and  the  outlet  approximately  so; 
the  temperature  of  the  inlet-water  is  noted,  the  read- 
ing of  the  gas-meter  taken,  and  at  this  same  time  the 
outlet-tube  changed  from  the  funnel  to  the  graduate. 


Io6  GAS  AND  FUEL  ANALYSIS. 

Ten  successive  readings  of  the  outflowing  water  are 
taken  while  the  graduate  (2-liter)  is  being  filled  and 
the  gas  shut  off. 

A  better  procedure  is  to  allow  the  water  to  run  into 
tared  8-liter  bottles,  three   being  used  for  a  test,  and 
weighing  the  water.     The  thermometer  in  the  outlet 
can  then  be  read  every  half-minute. 
EXAMPLE.  —  Temp,  of  incoming  water,  17.2° 
"       "  outgoing       "       43.8° 

Increase,  26.6° 

Gas  burned,  0.35  cu.  ft. 

liters  water  X  increase  of  temp.       2  X  26.6 
Heat  =  —  -  =  — 

cu.  ft.  gas  0.35 

=  152,30. 

From  burning  one  cubic  foot  of  gas  27.25  cc.  of 
water  were  condensed.  This  gives  off  on  an  average 
O.6  C.  per  cc. 

27.25  xo.6  =  i6.3  C.;  152  3-16.3  =  136  C.  per  cubic 
foot;  I36x3-96823  =  540  B.T.U. 


NOTES.  —  After  setting  up  the  apparatus  the  first 
thing  to  be  done  is  to  turn  on  the  water  —  (not  the  gas). 
Similarly,  the  water  should  be  shut  off  last.  All  con- 
nections and  the  meter  should  be  tested  for  leaks  be- 
fore each  test.  The  water  level  in  the  meter  should 
be  checked  daily.  Slight  drafts  caused  by  moving 
suddenly  near  the  apparatus  will  vary  outlet  readings 
and  vitiate  the  test.  The  instrument  should  not  be 
set  up  near  a  window  or  heating  apparatus  where 
radiant  heat  might  affect  the  readings. 

If  0.2  cu.  ft.  of  gas  are  burned,  then  an  error  of 
o.  i°  F.  in  temperature  of  water  means  an  error  of 
4  B.T.U.  ;  an  error  of  o.oi  Ib.  water,  0.9  B.T.U.; 
i°F.  in  gas  temperature,  1.8  B.T.U.;  o.  i  inch  (barom. 


FUEL  ANALYSIS— HEATING  VALUE.  107 

eter),  2   B.T.U.;    i    inch  water    pressure    of    gas,    1.5 
B.T.U.* 

The  calorific  power  obtained  without  subtracting 
the  heat  given  off  by  the  condensation  of  the  water 
represents  the  total  heating  value  of  the  gas.  This  is 
the  heat  given  off  when  the  gas  is  used  for  heating 
water  or  in  any  operation  where  the  products  of 
combustion  pass  off  below  100°  C.  The  net  heating 
value  represents  the  conditions  in  which  by  far  the 
greater  quantity  of  gas  is  consumed,  for  cooking, 
heating  and  gas  engines,  and  is  the  one  which  should 
be  reported.  It  should,  however,  be  corrected, -f^as- 
shown  on  page  no,  to  the  legal  cubic  foot,  that  is 
measured  at  30  inches  barometric  pressure,  and  60° 
F.  saturated  with  moisture. 

The  apparatus  has  been  tested  for  three  months 
in  the  German  Physical  Technical  Institute  with  hy- 
drogen, with  but  a  deviation  of  0.3  per  cent  from 
Thomson's  value.  This  value  may  vary  nearly  that 
amount  from  the  real  value  owing  to  the  method 
which  he  employed. 

b.  By  Calculation. 

Oftentimes  it  may  be  impracticable  to  determine 
the  heating  value  of  gases  directly;  in  such  cases 
recourse  must  be  had  to  the  calculation  of  its  calorific 
power  from  volumetric  analysis  of  the  gas. 

*  Kept.  Joint  Committee  on  Calorimetry  Public  Service  Commission 
and  Gas  Corporations  in  the  Second  Public  Service  District  of  New 
York  State  (1910),  p.  81. 

f  A  difference  of  i°  C.  or  of  3  mm.  pressure  makes  a  change  of  0.3 
per  cent  in  the  volume.  Pfeiffe,  J.  Gasbeleucht.,  50,  67  (1870). 


io8  GAS  AND  FUEL  ANALYSIS. 

To  this  end  multiply  the  percentage  of  each  con- 
stituent by  its  number  as  given  in  Table  IV,  and  the 
sum  of  the  products  will  represent  the  British  Thermal 
Units  evolved  by  the  combustion  of  one  cubic  foot  of 
the  gas.*  It  is  assumed  that  the  temperature  of  the 
gas  burned  and  the  air  for  combustion  is  60°  F.,  and 
that  of  the  escaping  gases  is  328°  P.,  that  correspond- 
ing to  the  temperature  of  steam  at  100  pounds  abso- 
lute pressure. 

As  has  been  already  stated,  column  3  in  Table  IV 
is  based  upon  the  assumption  that  the  gas,  and  air  for 
its  combustion,  enter  at  60°  F.,  and  the  products 
of  combustion  leave  at  328°  F. ;  in  column  4  it  is 
assumed  that  the  entering  temperature  of  both  gas 
and  air  is  32°  F.,  and  the  combustion-gases  are  cooled 
to  32°  F.  In  case  these  conditions  are  varied,  the 
amount  of  heat  which  the  gas  and  air  bring  in  must  be 
determined;  this  is  found  in  the  usual  way  by  multi- 
plying the  proportionate  parts  of  I  cubic  foot,  as 
shown  by  the  analysis,  by  the  specific  heat  of  the  gas, 
and  this  by  the  rise  in  temperature  (difference  between 
observed  temperature  and  32°  F.).  The  quantity  of 
air  necessary  for  combustion  is  found  by  multiplying 
the  percentage  composition  of  the  gas  by  the  number 
of  cubic  feet  necessary  for  the  combustion  of  each 
constituent. 

An  example  will  serve  to  make  this  clear.  The 
analysis  of  Boston  gas  is  as  follows :  f 

CO2       "Illuminatus."  O  CO  CII4  H  N 

2.9  15.0  o.o        25.3        25.9        27.9        3.0 

*  H.  L.  Payne,  Jour.  Analytical  and  Applied  Chem.,  7,  230. 
f  Jenkins,  Annual   Report  Inspector  of  Gas  Meters  and  Illuminat- 
ing Gas,  1896,  p.  ii. 


FUEL  ANALYSIS—  HEATING  VALUE.  109 

Or  in  one  cubic  foot  there  are 


.029  CO3 

.150  "illuminants"  ...........  279  H 

.253  CO.-  .................  ....     .030  N 

Let  us  assume  that  the  gases,  instead  of  passing 
out  at  a  temperature  of  328°  F.,  leave  at  the  same 
temperature  as  that  of  the  chimney-gases,  p.  29,  250° 
C.  or  482°  F. 

The  calculation  of  the  heat  carried  away  is  similar 
to  that  there  given. 
0.15    cu.   ft.  of  "  illuminants  "  produces,  Table   III, 

0.3  cu.  ft.  CO,  and  0.3  cu.  ft.  steam; 
0.253  cu.  ft.  of  carbonic  oxide  produces  .253  cu.  ft. 

C02; 
0.259  cu-  ft-  methane  produces  0.259  cu<  ft-  CO,  and 

.518  cu  ft.  steam; 
0.279  cu.  ft.  hydrogen  produces  .279  cu.  ft.  steam. 

From  the  combustion  of  the  gas  there  results  .812 
cu.  ft.  CO,,  1.097  cu.  ft.  steam,  and  5.90  X  79.08  or 
4.665  cu.  ft.  N. 

The  quantity  of  heat  they  carry  off  is  as  follows: 

Vol.  Vol.  Sp.  Ht.  Rise.  B.T.U. 

CO,  ............  812  X  .027    X    450=  9.9 

N  ............  4.66    X  .019    X    45°=  39-9 

Excess  of  air.  .    1.2       X  .019    X    450=  10.2 

Steam  .........    1.097  X  .0502  X  1229  =  67.7 

Total  heat  lost  ...............  =     127.7 

The  loss  due  to  the  steam  is  found  by  multiplying 
the  weight  of  steam  found  by  the  "  Total  Heat  of 


HO  GAS  AND  FUEL  ANALYSIS. 

Steam,"  as  found  from  Steam  Tables.*  The  tables, 
however,  do  not  extend  beyond  428°  F. ;  it  can  be 
calculated  by  the  formula 

Total  heat  =  A  =  1091.7  +  0.305^—  32). 

One  cubic  foot  of  hydrogen  when  burned  yields 
.0502  Ibs.  of  water. 

The  heat  generated  by  the  combustion  of  the  gas  is 
found  by  multiplying  its  volume  by  its  calorific  power, 
Table  IV. 

"  Illuminants" 0.15     X  2000.0  =  300.0  B.T.U. 

CO 0253X     341-2=    86.3 

CH4 0.259  x  1065.4=1276.0 

H 0.279  x     345-4=    96.3 


Heat  generated  by  the  gas 758-6  B.T.U. 

Total  heat  lost  (p.  109) ......    127.7 

630.9  B.T.U. 

This  figure,  630.9  B.T.U.,  represents  the  heating 
power  of  one  cubic  foot  of  the  gas  measured  at  62°  F., 
and  is  consequently  too  small;  its  heating  value  at 
32°  F.  is  represented  by 

492 4^"2  3°  X  630.9,  or  669.1  B.T.U. 

The  above  calculation,  like  all  giv'ng  accurate  results, 
is  somewhat  tedious;  a  shorter  and  less  correct  one  is  as 
follows:  Divide  the  figures  found  in  the  last  column  of 
Table  IV  of  the  Appendix  by  100,  the  result  gives  the 
heating  value  of  these  gases  in  B.T.U.  per  cubic  centi- 

*  Peabody's  Steam  Tables. 


FUEL  ANALYSIS— HEATING  VALUE.  in 

meter.*     According  to  the   volumetric  analysis  of  the 
gas  there  are  in  100  cc.  the  following: 

15.0  cc.  iliuminants, 
25.3  cc.  carbonic  oxide, 
25.90:.  methane, 
27.9  cc.  hydrogen. 
The  heating  value  is 

15.0X20.0  =300.0  B.T.U. 
25.3  X  3-4i=  86.3 
25.9X10.65  =276.0 

27-9  X  345=  96.3 

758.6  B.T.U. 

the  same  as  the  gross  heating  value  obtained  by  the  other 
method.     No  correction  is  applied  for  the  heat  lost. 

*  Method  followed  in  Prof.   Paper,  No.  48,  U.  S.  Geol.   Survey, 
Part  III,  p.  1005. 


APPENDIX. 


TABLE   I. 

TABLE  SHOWING  THE  TENSION  OF  AQUEOUS  VAPOR  AND  ALSO  THE 
WEIGHT  IN  GRAMS  CONTAINED  IN  A  CUBIC  METER  OF  AIR 
WHEN  SATURATED. 

From  5°  to  30°  C. 


Temp. 

Tension, 
mm. 

Grams. 

Temp. 

Tension, 
mm. 

Grams. 

Temp. 

Tension, 
mm. 

Grams. 

5 

6-5 

6.8 

14 

zi.g 

12.0 

23 

20.9 

20-4 

6 

7.0 

7-3 

15 

12.7 

12.8 

24 

22.2 

21-5 

7 

7-5 

7-7 

16 

13-5 

1.3-6 

25 

23.6 

22-9 

8 

8.0 

8.1 

17 

14.4 

M-5 

26 

25.0 

24.2 

9 

8.5 

8.8 

18 

15-4 

i5-i 

27 

26.5 

25.6 

10 

9.1 

9.4 

19 

16.3 

16.2 

28 

28.1 

27.0 

ii 

9.8 

10.  0 

20 

17.4 

17.2 

29 

29.8 

28.6 

12 

10.4 

10.6 

21 

18-5 

18.2 

30 

31-5 

29.2 

13 

11.  i 

"•3 

22 

19.7 

19-3 

TABLE   II. 

"VOLUMETRIC"  SPECIFIC  HEATS  OF  GASES.* 


Air 0.019 

Carbon  dioxide 0.027 

Carbonic  oxide 0.019 

Hydrogen 0.019 


"  Illuminants  " 0.040 

Methane.... 0.027 

Nitrogen 0.019 

Oxygen 0.019 


The  "volumetric"  specific  heat  is  the  quantity  of  heat  neces- 
sary to  raise  the  temperature  of  one  cubic  foot  of  gas  from  32°  F. 
to  33°  F. 

*  H.  L.  Payne,  Jour.  Anal,  and  Applied  Chem.,  7,  233. 


APPENDIX, 


TABLE  III. 

THE  VOLUME  OF  OXYGEN  AND  AIR  NECESSARY  TO  BURN  ONE  CUBIC 
FOOT  OF  CERTAIN  GASES,  TOGETHER  WITH  THE  VOLUME  OF  THE 
PRODUCTS  OF  COMBUSTION. 


Name. 

Formula. 

Volume 
of 
Oxygen. 

Volume* 
of 
Air. 

Volume 
of 
Steam. 

Volume 
of  Carbon 
Dioxide. 

Ignition 
Point 
Deg.  F. 

Hydrogen  .... 
Carbonic  oxide 
Methane  
Ethane 

H2 
CO 
CH4 
C2H6 

0-5 
0-5 
2.O 

•3     -I? 

2-39 
2-39 
9.56 
16  73 

I 
O 
2 

•2 

O 

I 
I 
2 

1085  || 

1200  || 
1230 

Propane 

C3H8 

50 

22   no 

JOT  C 

Butane  

6  5 

31  -O7 

c 

A 

Pentane. 

C5Hi2 

8  o 

78    24 

6 

Hexane  

C6H14 

9-  •> 

4$  -41 

7 

6 

1400 

Ethylenef  
PropyleneJ.  .  . 
Benzene  §  
Acetylene.  .  .  . 

C2H4 
C3H6 
C6H6 
C2H2 

3-o 
4-5 
7-5 

2-5 

14-34 
21.51 

35-85 

n-95 

2 

3 
3 

i 

2 

3 
6 

2 

IOIO  || 
940 

'788  || 

*Air   being    20.92    per    cent   by   volume,    4.78    volumes    contain 
i  volume  of  oxygen. 

fThe  chief  constituent  of  "illuminants,"  new  name  "ethene." 
J  New  name  "propene." 

§  Often  called  benzol,  not  to  be  confounded  with  benzine. 
H  Dixon  &  Coward,  Proc.  Chem.  Soc.,  26,  67. 


TABLES.  115 

TABLE    IV. 

CALORIFIC    POWER   OF   VARIOUS    GASES*  IN   BRITISH   THERMAL   UNITS 
PER    CUBIC    FOOT. 


Name. 

Symbol. 

60°  initial. 
328°  final.J 

32°  initial. 
32°  final. 

Hydrogen  

H 

26^.2 

OJC      A 

Carbonic  oxide  

CO 

qOO.Q 

•54.1  .2 

CH4 

8«i^.O 

1065.0 

i  700  .  o 

2OOO.O 

Ethane  .  •        .... 

C,H« 

1861  o 

Propane.  

C3H8 

26^7  o 

Buiane.  

'lAA  T  .O 

Pentane  

C*Hia 

42  «»5  .O 

C8HM 

5OI7.O 

Ethylene      . 

CoH* 

1674  o 

Propylene 

C3He 

2  COO  O 

Benzene   

CeHa 

4012  o 

Acetylene     

CijHa 

1477.  O 

*  H.  L.  Payne,  loc.  cit. 

f  Where  the  "illuminants"  are  derived  chiefly  from  the  decom- 
position of  mineral  oil. 

JThe  chief  constituent  of  the  "gasolene"  used  in  the  gas  machines 
for  carburetting  air. 

§  The  temperature  of  steam  at  100  Ibs.  absolute  pressure. 

TABLE  V. 

CALORIFIC  POWER  OF  VARIOUS  LIQUIDS  IN  BRITISH  THERMAL  UNITS  PER 

POUND. 


Name. 

B.  T.  U. 

Pounds  of  Air  for 
Combustion. 

Crude  petroleum,  Lima,  Ohio  

20,890 

Crude  petroleum,  Oil  Creek,  Pa  
Crude  petroleum,  heavy,  W.  Va  
63°  Be.  ^asolene 

21,600 
18,180 
19,162—20,448 

14  96* 

114°  F.  flash  kerosene 

18,643—19,802 

14  80* 

150°  fire-test  kerosene  

18,290 

Mineral  sperm  

20,065 

Ethyl  alcohol,  95  per  cent  

10,504 

Methyl  alcohol 

9e6<; 

Denatured  alcohol 

10,512—11,616 

8  13* 

*  BnHJ|43  Bureau  of  Mines,'i9i2,  pp.  18-21.  "Fuel  Values'of  Gasolene 
and  Denatured  Alcohol  in  Internal  Combustion  Engines.  "^ 


n6 


APPENDIX. 


TABLE  VI. 

CALORIFIC  POWER  OF  CERTAIN  SOLID  FUELS  IN  BRITISH  THERMAL  UNITS 
PER  POUND,   FIGURED   ON  THE  PURE  DRY  COMBUSTIBLE. 

Anthracite 13,740-15,620 

Bituminous  coal: 

Cumberland 16,320 

Georges  Creek 15,140 

Pocahontas 15,700 

West  Virginia i3,7°o 

Brown  coal 9,060-14,240 

Coke 13,880-14,560 

Peat 7,400-10,625 

Tanbark 6,100 

Wheat  straw 10,380 

Wood,  hard 8,500 

Wood,  pine 9>i5° 


TABLE  VII. 

SHOWING  THE  WEIGHT  OF  A  LITER  AND  SPECIFIC  GRAVITY  REFERRED 
TO    AIR,    OF    CERTAIN    GASES  AT    O°    C.    AND    760    MM. 


Name  of  Gas. 

Weight,  Grams. 

Specific  Gravity. 

Carbonic  oxide  

IOC  T 

I     966 

I     ^  IO 

o  0806 

o  060 

Methane  

Q.  71  C 

o  ^^^ 

Nitrogen  . 

I    2C.K 

I    A."\Q 

I    105 

Air  

I     2QJ. 

I    OOO 

TABLES.  117 

TABLE  VIII. 

SOLUBILITY   OF   VARIOUS    GASES    IN   WATER. 

One  volume  of  water  at  20°  C.  absorbs  the  following  volumes  of 
gas  reduced  to  o°  C.  and  760  mm.  pressure. 


Name  of  Gas. 

Symbol. 

Volumes. 

Carbonic  oxide  

CO 

o  023 

COo 

Ho 

CH4 

O.O'ie. 

No 

o  014 

O2 

o  028 

Air     

O   OI  7 

TABLE  IX. 


MELTING-POINTS    OF    VARIOUS    METALS    AND    SALTS,    FOR    USE    WITH 
APPARATUS    FIG.   II. 

By  Temperatures. 
C.      Tin 232 


Alphabetically. 

Aluminium 658 

Antimony 630 

fBarium  chloride 950 

Bismuth 270 

Calcium  fluoride 902 

Cadmium 302 

fCadmium  chloride 541 

Copper 1083 

Lead 327 

fPotassium  bromide. . .  .  740 

fPotassium  chloride ....  780 

fSodium  bromide 748 

fSodium  carbonate 853 

Tin 232 

Zinc. 419 


Tin 232°  C.* 

Bismuth 270* 

Cadmium 302* 

Lead 327* 

Zinc 419* 

Cadmium  chloride 54 1 1 

Antimony 630* 

Aluminium 658* 

Potassium  bromide 740* 

Sodium  bromide 748* 

Potassium  chloride 780* 

Sodium  carbonate 853* 

Calcium  fluoride 902  § 

Barium  chloride 95°* 

Copper 1083* 


*  Burgess-Le  Chatelier,  Measurement  of  High  Temperatures,  1912. 
t  These  salts  must  be  dried  at  105°  C.  to  a  constant  weight. 
J  Carnelley,  Melting-  and  Boiling-point  Tables. 
§  Meyer,  Riddle  and  Lamb,  Ber.  d.  deut.  Chem.  Gesellsch.,  27, 
3140  (1894). 


n8 


APPENDIX. 


TABLE  X. 

GIVING    THE    NUMBER    OF    TIMES     THE    THEORETICAL   QUANTITY    OF 
AIR    SUPPLIED,    WITH    VARIOUS    GAS    ANALYSES.* 


c&+ 

N  =  79. 
C02+0-fCO=2i 

N  =  8o. 
CO2-f-O+CO=2o. 

N  =  81. 
C02-K>+CO=i9. 

N  =  82. 
CO2-KH-CO  =  i8. 

21 

.00 

20 

.05 

.00 

.... 

.... 

19 

.10 

•05 

.00 

.... 

18 

•  17 

.10 

•05 

.OO 

17 

•  23 

.16 

.10 

•05 

16 

•  31 

•  23 

.16 

.10 

15 

.40 

•  31 

•  23 

.16 

14 

•  50 

•39 

•  30 

.22 

13 

.61 

•49 

•39 

•30 

12 

•75 

.60 

.48 

.38 

II 

.91 

•73 

1-59 

•47 

10 

2.IO 

1.89 

1.72 

•58 

9 

2-33 

2.07 

1.87 

.70 

8 

2.62 

2.29 

2.04 

•85 

7 

3-00 

2-57 

2.26 

2.  02 

6 

3-50 

2.92 

2.52 

2.23 

5 

4.2O 

3-39 

2.86 

2.48 

4 

5-25 

4-05 

3-30 

2-79 

3 

7.OO 

5-oo 

3-89 

3-20 

2 

10.50 

6.53 

4-76 

3-76 

I 

21  .OO 

9-43 

6.10 

4-54 

*  Coxe,  Proc.  N.  E.  Cotton  Manufacturers'  Assoc.,  1895. 


TABLE  XI. 

COMPARISON   OF  METRIC  AND  ENGLISH   SYSTEMS. 

i  cubic  inch          =16.39  c-c- 
i  cubic  foot  =28.315  liters, 

i  cubic  meter        =35.32  cu.  ft. 
i  Imperial  gallon  =  4.543  liters. 


i  Ib.  avoirdupois =453. 593  grams. 

i  calorie  =     3.969  B.T.U.  (Rontgen). 


COAL  AND  FUEL  OIL  SPECIFICATIONS.          119 


COAL  AND  FUEL  OIL  SPECIFICATIONS. 

COAL  SPECIFICATIONS. 

The  following,  from  Bulletin  339,  U.  S.  Geological  Survey  (1908),  by 
D.  T.  Randall,  will  give  an  idea  of  some  coal  specifications: 

SPECIFICATIONS  FOR  THE  U.  S.  GOVERNMENT  FUEL 
SUPPLY  AS  APPROVED  BY  THE  NATIONAL  ADVISORY 
BOARD  ON  FUELS  AND  STRUCTURAL  MATERIALS, 
MARCH,  1907. 

SPECIFICATIONS  AND  PROPOSALS  FOR  SUPPLYING  COAL. 

United  States 

,  190 

PROPOSAL. 

Sealed  proposals  will  be  received  at  this  office  until  2  o'clock  P.M., 

190. .,  for  supplying  coal  to  the  United  States building 

at. .  , .  as  follows: 


The  quantity  of  coal  stated  above  is  based  upon  the  previous  annual 
consumption,  and  proposals  must  be  made  upon  the  basis  of  a  delivery 
of  10  per  cent  more  or  less  than  this  amount,  subject  to  the  actual 
requirements  of  the  service. 

Proposals  must  be  made  on  this  form,  and  include  all  expenses 
incident  to  the  delivery  and  stowage  of  the  coal,  which  must  be  delivered 
in  such  quantities  and  at  such  times  within  the  fiscal  year  ending 
June  30,  190. .,  as  may  be  required. 

Proposals  must  be  accompanied  by  a  deposit  (certified  check,  when 

practicable,  in  favor  of )  amounting  to  10  per  cent 

of  the  aggregate  amount  of  the  bid  submitted,  as  a  guaranty  that  it  is 
bona  fide.  Deposits  will  be  returned  to  unsuccessful  bidders  imme- 
diately after  award  has  been  made,  but  the  deposit  of  the  successful 
bidder  will  be  retained  until  after  the  coal  shall  have  been  delivered 
and  final  settlement  made  therefor,  as  security  for  the  faithful  per- 
formance of  the  terms  of  the  contract,  with  the  understanding  that 
the  whole  or  a  part  thereof  may  be  used  to  liquidate  the  value  of  any 


120  APPENDIX. 

deficiencies  in  quality  or  delivery  that  may  arise  under  the  terms  of 
the  contract. 

When  the  amount  of  the  contract  exceeds  $10,000,  a  bond  may  be 
executed  in  the  sum  of  25  per  cent  of  the  contract  amount,  and  in  this 
case  the  deposit  or  certified  check  submitted  with  the  proposal  will 
be  returned  after  approval  of  the  bond. 

The  bids  will  be  opened  in  the  presence  of  the  bidders,  their  repre- 
sentatives, or  such  of  them  as  may  attend,  at  the  time  and  place  above 
specified. 

In  determining  the  award  of  the  contract,  consideration  will  be 
given  to  the  quality  of  the  coal  offered  by  the  bidder,  as  well  as  the 
price  per  ton,  and  should  it  appear  to  the  best  interests  of  the  Govern- 
ment to  award  the  contract  for  supplying  coal  at  a  price  higher  than 
that  named  in  lower  bid  or  bids  received,  the  award  will  be  so  made. 

The  right  to  reject  any  or  all  bids  and  to  waive  defects  is  expressly 
reserved  by  the  Government. 

DESCRIPTION  OF  COAL  DESIRED.* 

Bids  are  desired  on  coal  described  as  follows: 


Coals  containing  more  than  the  following  percentages,  based  upon 
dry  coal,  will  not  be  considered: 

Ash per  cent 

Volatile  matter per  cent 

Sulphur per  cent 

Dust    and    fine    coal    as    delivered    at   point    of 

consumption  f per  cent 

DELIVERY 

The  coal  shall  be  delivered  in  such  quantities  and  at  such  times  as 
the  Government  may  direct. 

In  this  connection  it  may  be  stated  that  all  the  available  storage 
capacity  of  the  coal  bunkers  will  be  placed  at  the  disposal  of  the  con- 
tractor to  facilitate  delivery  of  coal  under  favorable  conditions. 

*  This  information  will  be  given  by  the  Government  as  may  be  determined 
by  boiler  and  furnace  equipment,  operating  conditions,  and  the  local    market, 
t  All  coal  which  will  pass  through  a  J-inch  round-hole  screen. 


COAL   AND  FUEL   OIL  SPECIFICATIONS.         121 

After  verbal  or  written  notice  has  been  given  to  deliver  coal  under 
this  contract,  a  further  notice  may  be  served  in  writing  upon  the  con- 
tractor to  make  delivery  of  the  coal  so  ordered  within  twenty-four 
hours  after  receipt  of  said  second  notice. 

Should  the  contractor,  for  any  reason,  fail  to  comply  with  the  second 
request,  the  Government  will  be  at  liberty  to  buy  coal  in  the  open 
market,  and  to  charge  against  the  contractor  any  excess  in  price  of 
coal  so  purchased  over  the  contract  price. 

SAMPLING. 

Samples  of  the  coal  delivered  will  be  taken  by  a  representative  of 
the  Government. 

In  all  cases  where  it  is  practicable,  the  coal  will  be  sampled  at  the 
time  it  is  being  delivered  to  the  building.  In  case  of  small  deliveries, 
it  may  be  necessary  to  take  these  samples  from  the  yards  or  bins.  The 
sample  taken  will  in  no  case  be  less  than  the  total  of  100  Ibs.,  to  be 
selected  proportionally  from  the  lumps  and  fine  coal,  in  order  that 
it  will  in  every  respect  truly  represent  the  quantity  of  coal  under  con- 
sideration. 

In  order  to  minimize  the  loss  in  the  original  moisture  content  the 
gross  sample  will  be  pulverized  as  rapidly  as  possible  until  none  of 
the  fragments  exceed  one-half  inch  in  diameter.  The  fine  coal  will 
then  be  mixed  thoroughly  and  divided  into  four  equal  parts.  Opposite 
quarters  will  be  thrown  out,  and  the  remaining  portions  thoroughly 
mixed  and  again  quartered,  throwing  out  opposite  quarters  as  before. 
This  process  will  be  continued  as  rapidly  as  possible  until  the  final 
sample  is  reduced  to  such  amount  that  all  of  the  final  sample  thus 
obtained  will  be  contained  in  the  shipping  can  or  jar  and  sealed  air- 
tight. 

The  sample  will  then  be  forwarded  to 

If  desired  by  the  coal  contractor,  permission  will  be  given  to  him, 
or  his  representative,  to  be  present  and  witness  the  quartering  and 
preparation  of  the  final  sample  to  be  forwarded  to  the  Government 
laboratories. 

Immediately  on  receipt  of  the  sample,  it  will  be  analyzed  and  tested 
by  the  Government,  folio  whig  the  method  adopted  by  the  American 
Chemical  Society,  and  using  a  bomb  calorimeter.  A  copy  of  the  result 
will  be  mailed  to  the  contractor  upon  the  completion  thereof. 


122  APPENDIX. 


CAUSES  FOR  REJECTION. 

A  contract  entered  into  under  the  terms  of  this  specification  shall 
not  be  binding  if,  as  the  result  of  a  practical  service  test  of  reasonable 
duration,  the  coal  fails  to  give  satisfactory  results  owing  to  excessive 
clinkering  or  to  a  prohibitive  amount  of  smoke. 

It  is  understood  that  the  coal  delivered  during  the  year  will  be  of 
the  same  character  as  that  specified  by  the  contractor.  It  should, 
therefore,  be  supplied,  as  nearly  as  possible,  from  the  same  mine  or 
group  of  mines. 

Coal  containing  percentages  of  volatile  matter,  sulphur,  and  dust 
higher  than  the  limits  indicated  on  page  2  and  coal  containing  a  per- 
centage of  ash  in  excess  of  the  maximum  limits  indicated  in  the  follow- 
ing table  will  be  subject  to  rejection. 

In  the  case  of  coal  which  has  been  delivered  and  used  for  trial,  or 
which  has  been  consumed  or  remains  on  the  premises  at  the  time  of 
the  determination  of  its  quality,  payment  will  be  made  therefor  at  a 
reduced  price,  computed  under  the  terms  of  this  specification. 

Occasional  deliveries  containing  ash  up  to  the  precentage  indicated 
in  the  column  of  "Maximum  limits  for  ash,"  on  page  4,  may  be 
accepted.  Frequent  or  continued  failure  to  maintain  the  standard 
established  by  the  contractor,  however,  will  be  considered  sufficient 
cause  for  cancellation  of  the  contract. 

PRICE  AND  PAYMENT.* 

Payment  will  be  made  on  the  basis  of  the  price  named  in  the  pro- 
posal for  the  coal  specified  therein,  corrected  for  variations  in  heating 
value  and  ash,  as  shown  by  analysis,  above  and  below  the  standard 
established  by  contractor  in  this  proposal.  For  example,  if  the  coal 
contains  2  per  cent,  more  or  less,  British  thermal  units  than  the  estab- 
lished standard,  the  price  will  be  increased  or  decreased  2  per  cent 
accordingly. 

The  price  will  also  be  further  corrected  for  the  percentages  of  ash. 
For  all  coal  which  by  analysis  contains  less  ash  than  that  established 

*  The  economic  value  of  a  fuel  is  affected  by  the  actual  amount  of  com- 
bustible matter  it  contains,  as  determined  by  its  heating  value  shown  in  British 
thermal  units  per  pound  of  fuel,  and  also  by  other  factors,  among  which  is  its 
ash  content.  The  ash  content  not  only  lowers  the  heating  value  and  decreases 
the  capacity  of  the  furnace,  but  also  materially  increases  the  cost  of  handling 
the  coal,  the  labor  of  firing,  and  the  cost  of  removal  of  ashes,  etc. 


COAL   AND  FUEL  OIL  SPECIFICATIONS. 


123 


in  this  proposal  a  premium  of  i  per  cent  per  ton  for  each  whole  per 
cent  less  ash  will  be  paid.  An  increase  in  the  ash  content  of  2  per  cent 
over  the  standard  established  by  contractor  will  be  tolerated  without 
exacting  a  penalty  for  the  excess  of  ash.  When  such  excess  exceeds 
2  per  cent  above  the  standard  established,  deductions  will  be  made 
from  the  price  paid  per  ton  in  accordance  with  following  table: 


i§2 

Cents  per  Ton  to  be  Deducted. 

i 

Ash  as     +5  £ 

ij^j 

Establish-  3-3  £: 

P-Si 

edin  Pro-  -g      ° 
posal  (PerQ  OjS 

2 

4 

7 

12 

18 

25 

35 

!•§ 

Cent). 

*  jo 

2- 

Percentages  of  Ash  in  Dry  Coal. 

5 

7 

7-8 

8-9 

9-IO 

IO-II 

11-12 

12-13 

13-14 

12 

6 

8 

8-9 

9-10 

IO-II 

11-12 

12-13 

13-14 

14-15 

13 

7 

9 

9-10 

IO-II 

11-12 

12-13 

13-14 

14-15 

15-16 

14 

8 

10 

10-11 

11-12 

12-13 

13-14 

14-15 

15-16 

16-17 

14 

9 

ii 

11-12 

12-13 

13-14 

14-15 

IS-I6 

16-17 

I7-I8 

15 

10 

12 

12-13 

13-14 

14-15 

I5-I6 

16-17 

I7-I8 

16 

n 

13 

13-14 

14-15 

15-16 

1  6—  17 

I7-l8 

18-19 

16 

12 

14 

14-15 

I5-I6 

16-17 

17-18 

iS-IQ 

19-20 

i? 

13 

1C 

iz—  1  6 

16—  17 

I7-l8 

1  8-iQ 

IQ—  2O 

2O—  21 

18 

14 

16 

16-17 

17-18 

18-19 

19-20 

2O-2I 

21-22 

IQ 

15 

17 

17-18 

18-19 

19—20 

2O—  21 

21—22 

IQ 

16 

18 

18-10 

IQ—  2O 

2O—  21 

21—22 

22—23 

2O 

17 

19 

19-20 

2O-2I 

21-22 

22-2"? 

21 

18 

20 

2O-2I 

21-22 

22-23 

22 

Proposals   to  receive   consideration  must   be   submitted  upon   this 
form  and  contain  all  of  the  information  requested. 


,  190.. 

The  undersigned  hereby  agree  to  furnish  to  the  U.  S 

building  at  ,  the  coal  described,  in  tons  of  2,240  Ibs. 

each  and  in  quantity  10  per  cent  more  or  less  than  that  stated  on 
page  i,  as  may  be  required  during  the  fiscal  year  ending  June  30, 
100.  .,  in  strict  accordance  with  this  specification;  the  coal  to  be  de- 
livered in  such  quantities  and  at  such  times  as  the  Government  may 
direct. 


124 


APPENDIX. 


Item  No.  .  . 

Item  No.  .  . 

Item  No... 

Description. 
Commercial  name  

Name  of  mine      .  .  . 

Location  of  mine  

Name  of  coal  bed  

Size    of    coal    (if    coal    is 
screened)  : 
Coal    to    pass   through 
openings  

Coal  to  pass  over  open- 
ings   

Data  to  establish  a  basis  for 
payment. 
Per  cent  of  ash  in  dry  coal 
(method    of    American 
Chemical  Society)  

.  inches  -j  round 
|  square 
.  inches  J  bar 

.  .  inches  -j  round 
|  square 
.  .  inches  J  bar 

.  .  inches  -j  round 
1  square 
.  .  inches  J  bar 

British   thermal   units   in 
coal  as  delivered  

Price  per  ton  (2,240  Ibs.)  .  . 

• 

It  is  important  that  the  above  information  does  not  establish  a  higher 
standard  than  can  be  actually  maintained  under  the  terms  of  the  contract; 
and  in  this  connection  it  should  be  noted  that  the  small  samples  taken  from 
the  mine  are  invariably  of  higher  quality  than  the  coal  actually  delivered 
therefrom.  It  is  evident,  therefore,  that  it  will  be  to  the  best  interests  of  the 
contractor  to  furnish  a  correct  description  with  average  values  of  the  coal 
offered,  as  a  failure  to  maintain  the  standard  established  by  contractor  will 
result  in  deductions  from  the  contract  price,  and  may  cause  a  cancellation  of 
the  contract,  while  deliveries  of  a  coal  of  higher  grade  than  quoted  will  be 
paid  for  at  an  increased  price. 

Signature 

Address.  . 


Name  of  corporation 

Name  of  president 

Name  of  secretary 

Under  what  law  (State)  corporation  is  organized 


As  will  be  seen  from  the  foregoing  specification,  the  bidder  is  not 
required  to  submit  a  sample  of  his  coal,  but  is  expected  to  name  a 
standard  of  British  thermal  units  in  the  coal  as  it  is  to  be  delivered. 
This  value  is  made  the  basis  for  purchase,  because  a  correction  is  thus 
made  for  the  amount  of  moisture  in  the  coal.  It  should  be  noted  that 
this  value  will  in  all  cases  be  lower  than  the  British  thermal  units  in 
the  dry  coal,  which  is  usually  given  in  connection  with  the  coal  analysis. 
The  percentage  of  ash  is  also  specified,  as  it  is  a  factor  in  the  successful 
burning  of  the  coal  on  the  grate  and  as  it  involves  an  expense  for 
removal  from  the  premises. 


COAL  AND   FUEL  OIL  SPECIFICATIONS. 


I25 


The  following  are  the  essential  features  of  the  contracts  on  which 
a  Chicago  company  is  said  to  purchase  and  inspect  nearly  1,000,000 
tons  of  coal  for  its  clients  in  Chicago,  Indianapolis,  Minneapolis, 
St.  Louis,  and  other  cities: 

I.  The  company  agrees  to  furnish  and  deliver  to  the  consumer 

at  such  times  and  in  such  quantities  as  ordered  by  the 

consumer  for  consumption  at  said  premises  during  the  term  hereof, 
at  the  consumer's  option,  either  or  all  of  the  kinds  of  coal  described 
below;  said  coals  to  average  the  following  assays: 


Kind  of  coal  

Of  size  passing  through  screen  having  circu- 
lar perforations  in  diameter  

....  inches 

....  inches 

....  inches 

Of  size  passing  over  a  screen  having  circular 

inches 

Per  cent  of  moisture  in  coal  as  delivered  .  . 

Per  cent  of  ash  in  coal  as  delivered    

British  thermal  units  per  pound  of  dry  coal. 

From  following  county      

Coal  of  the  above  respective  descriptions  and  specified  assays  (not 
average  assays)  to  be  hereinafter  known  as  the  contract  grade  of  the 
respective  kinds. 

II.  The  consumer  agrees  to  purchase  from  the  company  all  the  coal 
required  for  consumption  at  said  premises  during  the  term  of  said 
contract,  except  as  set  forth  in  Paragraph  III  below,  and  to  pay  the 
company  for  each  ton  of  2000  Ibs.  avoirdupois  of  coal  delivered  and 
accepted  hi  accordance  with  all  the  terms  of  this  contract  at  the  follow- 
ing contract  rate  per  ton  for  coal  of  each  respective  contract  grade, 
at  which  rates  the  company  will  deliver  the  following  respective  numbers 
of  British  thermal  units  for  i  cent,  the  contract  guaranty: 


Contract 

Kind  of  Coal. 

Rate  per 

Contract  Guaranty. 

Ton. 

, 

$.. 

equal  to 

net  B  T  U   for 

$  

equal  to. 

net  B.T.U.  for 

i  cent 

$  

equal  to  . 

net  B  T  U  for 

Said  net  British  thermal  units  for  i  cent  being  in  each  case  deter- 
mined as  follows:  Multiply  the  number  of  British  thermal  units  per 
pound  of  dry  coal  by  the  per  cent  of  moisture  (expressed  in  decimals), 


126  APPENDIX. 

subtract  the  product  so  found  from  the  number  of  British  thermal  units 
per  pound  of  dry  coal,  multiply  the  remainder  by  2000,  and  divide 
this  product  by  the  contract  rate  per  ton  (expressed  in  cents)  plus 
one-half  of  the  ash  percentage  (expressed  as  cents). 

III.  It  is  provided  that  the  consumer  may  purchase  for  consumption 
at  said  premises  coal  other  than  herein  contracted  for,  for  test  purposes, 
it  being  understood  that  the  total  of  such  coal  so  purchased  shall  not 
exceed  5  per  cent  of  the  total  consumption  during  the  term  of  this 
contract. 

IV.  It  is  understood  that  the  company  may  deliver  coal  hereunder 
containing  as  high  as  3  per  cent  more  ash  and  as  high  as  3  per  cent 
more  moisture  and  as  low  as  500  fewer  British  thermal  units  per  pound 
dry  than  specified  above  for  contract  grades. 

V.  Should   any    coal   delivered   hereunder   contain   more   than    the 
per  cent  of  ash  or  moisture  or  fewer  than  the  number  of  British  thermal 
units  per  pound  dry  allowed  under  Paragraph  IV  hereof,  the  con- 
sumer may,  at  its  option,  either  accept  or  reject  same. 

VI.  All  coal  accepted  hereunder  shall  be  paid  for  monthly  at  a  price 
per  ton  determined  by  taking  the  average  of  the  delivered  values 
obtained  from  the  analyses  of  all  the  samples  taken  during  that  month, 
said  delivered  value  in  each  case  being  obtained  as  follows:    Multiply 
the  number  of  British  thermal  units  delivered  per  pound  of  dry  coal 
by  the  per  cent  of  moisture  delivered  (expressed  in  decimals),  subtract 
the  product  so  found  from  the  number  of  British  thermal  units  delivered 
per  pound  of  dry  coal,  multiply  the  remainder  by  2000,  divide  this 
product  by  the  contract  guaranty,  and  from  this  quotient  (expressed 
as  dollars  and  cents)  subtract  one-half  of  the  ash  percentage  delivered 
(expressed  as  cents). 

The  following  are  the  essential  features  of  the  specifications  used 
by  the  Interborough  Rapid  Transit  Company  of  New  York  in  pur- 
chasing about  30,000  tons  of  coal  each  month  for  use  in  its  plants, 
which  are  among  the  largest  in  the  United  States: 

PRELIMINARY  SPECIFICATIONS  FOR  BITUMINOUS  COAL  FOR  THE  INTER- 
BOROUGH  RAPID  TRANSIT  COMPANY. 

Coal  must  be  a  good  steam,  caking,  run-of-mine,  bituminous  coal  free 
from  all  dirt  and  excessive  dust,  a  dry  sample  of  which  will  approximate 
the  company's  standard  in  heat  value  and  analysis  as  follows:  Carbon, 
71;  volatile  matter,  20;^  ash,  9;  B.T.U.,  14,100;  sulphur,  1.50. 


COAL   AND  FUEL  OIL    SPECIFICATIONS.          127 

A  small  quantity  of  coal  will  be  taken  from  each  weighing  hopper 
just  before  the  hopper  is  dumped  while  the  lighter  is  being  unloaded. 
These  quantities  will  be  thrown  into  a  receptacle  provided  for  the 
purpose,  and  when  the  lighter  is  empty  the  contents  of  the  receptacle 
will  be  thoroughly  mixed,  and  a  sample  of  this  mixture  will  be  taken 
for  chemical  analysis.  This  average  sample  of  coal  will  be  labeled  and 
held  for  one  week  after  the  unloading  of  the  lighter.  The  sample  taken 
from  the  mixture  for  test  will  be  analyzed  as  soon  as  possible  after 
being  taken.  No  other  sample  will  be  recognized. 

Tests  of  sample  taken  from  average  sample  will  be  made  by  the 
company's  chemist  under  the  supervision  of  the  superintendent. 
Should  the  contractor  question  the  results  of  the  company's  test  (a 
copy  of  which  will  be  mailed  to  him),  the  company  will,  if  requested 
by  the  contractor  within  three  days  after  copy  of  test  has  been  mailed 
to  him,  forward  sufficient  quantity  of  the  average  sample  taken  from 
each  weighing  hopper  to  any  laboratory  in  the  city  of  New  York  which 
may  be  agreed  upon  by  the  superintendent  and  the  contractor,  and 
have  said  sample  analyzed  by  it,  and  the  results  obtained  from  this 
second  test  will  be  considered  as  final  and  conclusive.  In  case  the 
disputed  values,  as  obtained  in  the  company's  test,  shall  be  found  by 
the  second  test  to  be  2  per  cent  or  less  in  error,  then  the  cost  of  said 
second  test  shall  be  borne  by  the  contractor;  but  if  the  disputed 
values  shall  be  found  to  be  more  than  2  per  cent  in  error,  then  the  cost 
of  said  second  test  shall  be  borne  by  the  company. 

Should  there  be  no  question  raised  by  the  contractor  within  the 
three  days  specified,  as  to  the  values  of  the  first  analysis,  the  average 
sample  of  coal  will  be  destroyed  at  the  end  of  seven  days  from  date  of 
discharge  of  coal  from  lighter.  Should  a  second  test  be  made  of  coal 
taken  from  any  lighter  as  herein  provided,  then  any  penalties  to  be 
made  as  set  forth  in  paragraph  under  "  Penalties"  will  be  based  on 
the  results  as  obtained  from  the  second  test. 

The  price  to  be  paid  by  the  company  per  ton  per  lighter  of  coal  will 
be  based  on  a  table  of  heat  values  for  excess  or  deficiency  of  its  standard, 
but  subject  to  deductions  as  given  in  the  section  under  "Penalized 
coal,"  including  excess  of  ash,  volatile  matter,  sulphur,  or  dust,  or  less 
than  the  minimum  amount  required  to  be  contained  in  any  lighter, 
for  coal  which  shows  results  less  than  the  company's  standard. 

Premiums  or  deductions  are  based  on  a  rate  of  i  cent  per  ton  for  a 
variation  of  50  B.T.U.  per  pound  of  coal,  as  indicated  in  a  table  a 
few  items  of  which  are  given  below: 


128  APPENDIX. 

Table  f or  B.T.U.  Values. 

For  coal  in  any  lighter  which  is  found  by  test  to  contain,  per  pound 
of  dry  coal,  from 

15,501  and  above 28  cents  per  ton  above  standard 

15,101  to  15,150,  both  inclusive 20  cents  per  ton  above  standard 

14,601  to  14,650,  both  inclusive 10  cents  per  ton  above  standard 

14,101  to  14,150,  both  inclusive Standard 

13,601  to  13,650,  both  inclusive 10  cents  per  ton  below  standard 

13,101  to  13,150,  both  inclusive 20  cents  per  ton  below  standard 

12,101  to  12,150,  both  inclusive 40  cents  per  ton  below  standard 

No  lighter  of  coal  will  be  accepted  which,  by  trial,  in  the  judgment 
of  the  superintendent,  contains  an  excessive  amount  of  dry  coal  dust. 
The  decision  of  the  superintendent  will  be  final  in  this  respect.  Coal 
taken  from  such  lighter  for  trial  will  be  subject  to  the  special  deduction 
set  forth  under  "Penalized  coal,"  but  paid  for  in  all-  other  respects  as 
herein  provided. 

Coal  which  is  shown  by  analysis  to  contain  less  than  20  per  cent  of 
volatile  matter,  9  per  cent  of  ash,  or  1.50  per  cent  of  sulphur,  will  be 
accepted,  without  a  deduction  from  the  bidder's  price,  plus  or  minus 
an  amount  for  excess  or  deficiency  of  British  thermal  unit  value,  as 
herein  provided.  Where  the  analysis  gives  amounts  for  any  or 'all 
elements  in  excess  of  these  quantites,  deductions  will  be  made  from 
the  bidder's  price  in  accordance  with  the  tables  of  values  of  volatile 
matter,  ash,  and  sulphur  below  given,  plus  or  minus  the  amount  for 
excess  or  deficiency  of  the  standard  British  thermal  unit  value,  in 
addition  to  any  other  deductions  which  may  be  made  as  herein  pro- 
vided. 

Table  of  Deductions  for  Volatile  Matter. 

For  coal  in  any  lighter  which  is  found  by  test  to  contain,  per  pound  of 
dry  coal 

Over  20  per  cent  and  less  than  21  per  cent 2  cents  per  ton 

********* 

Over  22.5  per  cent  and  less  than  23  per  cent 12  cents  per  ton 

********* 
24  per  cent  and  over X8  cents  per  ton 

,  This  table  is  made  for  the  difference  of  each  one-half  of  i  per  cent 
and  the  deductions  are  at  the  rate  of  4  cents  for  each  I  per  cent  of 
volatile  matter. 


COAL   AND  FUEL  OIL  SPECIFICATIONS.          129 

Table  of  Deductions  for  Ash. 

For  coal  in  any" lighter  which  is  found  by  test  to  contain,  per  pound  of 
dry  coal 

Over  9  per  cent  and  less  than  9.5  per  cent 2  cents  per  ton 

********* 

Over  11.5  per  cent  and  less  than  12 12  cents  per  ton 

********* 

13.5  per  cent  and  over 23  cents  per  ton 

This  table  is  made  for  each  difference  of  one-half  of  i  per  cent  and 
at  the  rate  of  4  cents  for  each  i  per  cent  increase  in  the  ash. 

Table  of  Deductions  for  Sulphur. 

For  coal  in  any  lighter  which  is  found  by  test  to  contain,  per  pound  of 
dry  coal 

Over  1.50  per  cent  and  less  than  1.75  per  cent  .  .     6  cents  per  ton 
********* 

Over  2  per  cent  and  less  than  2.25  per  cent 10  cents  per  ton 

********* 

2.50  and  over 20  cents  per  ton 

This  table  is  made  out  for  each  difference  of  one-fourth  of  i  per  cent 
and  at  a  diminishing  rate. 

Should  any  lighter  of  coal  delivered  at  the  company's  docks  contain 
less  than  700  tons,  a  deduction  of  7  cents  per  ton  will  be  made  from 
the  price  as  determined  by  the  British  thermal  unit  value  and  analysis, 
in  addition  to  any  other  penalty  provided  for  herein.  Should  any 
lighter  of  coal  delivered  at  the  company's  docks  be  rejected  by  the  super- 
intendent on  account  of  excessive  amount  of  coal  dust,  then  a  reduction 
of  25  cents  per  ton  will  be  made  from  the  price  as  determined  by  the 
British  thermal  unit  value  and  analysis,  for  the  coal  taken  from  said 
lighter,  in  addition  to  any  other  penalty  which  may  be  made  as  herein 
provided.  Should  any  lighter  of  coal  be  delivered  in  other  than  self- 
trimming  lighters  as  herein  provided,  a  deduction  of  7  cents  per  ton 
will  be  made  from  the  price  as  determined  by  the  British  thermal  unit 
value  and  analysis,  exclusive  of  any  other  penalty  which  may  be  made 
as  herein  provided. 

The  contractor's  bill  of  lading  will  be  checked  by  the  company's 
scales.  Should  there  be  a  deficiency  of  i  per  cent  or  more  between 


130  APPENDIX. 

the  bill  of  lading  and  the  company's  weights,  then  the  company's 
weights  will  be  taken  as  correct. 

When  the  contractor  has  been  notified  by  the  company  to  deliver 
coal  under  this  contract,  a  further  notice  may  be  given  requiring  the 
contractor  to  make  delivery  of  the  coal  so  ordered  within  twelve  hours 
after  the  receipt  of  said  second  notice.  Should  the  contractor,  for  any 
reason,  fail  to  deliver  the  coal  so  ordered  within  twelve  hours  after 
the  receipt  of  said  second  notice  and  in  accordance  with  the  require- 
ments therein  as  to  place  of  delivery,  the  company  shall  be  at  liberty 
to  buy  coal  in  the  open  market,  and  the  contractor  will  make  good 
to  the  company  any  difference  there  may  be  between  the  price  paid 
by  the  company  for  said  coal  in  open  market  and  the  price  the  com- 
pany would  have  paid  to  the  contractor  had  the  coal  been  delivered 
by  it  in  accordance  with  the  requirements  of  said  notices  from  the 
company,  or  said  difference  may  be  deducted  from  any  money  then 
due  or  thereafter  to  become  due  to  the  contractor  under  the  contract 
to  be  entered  into. 


FUEL  OIL  SPECIFICATIONS. 
The  Specifications  of  the  U.  S.  Government  are  as  follows*: 

GENERAL  SPECIFICATIONS. 

(1)  In  determining  the  award  of  a  contract,  consideration  will  be 
given  to  the  quality  of  the  fuel  offered  by  the  bidders,  as  well  as  tha 
price,  and  should  it  appear  to  be  to  the  best  interest  of  the  Govern- 
jnent  to  award  a  contract  at  a  higher  price  than  that  named  in  the 
lowest  bid  or  bids  received,  the  contract  will  be  so  awarded. 

(2)  Fuel  oil  should  be  either  a  natural  homogeneous  oil  or  a  homo- 
geneous residue  from  a  natural  oil ;   if  the  latter,  all  constituents  having 
a  low  flash-point  should  have  been  removed  by  distillation;    it  should 
not  be  composed  of  a  light  oil  and  a  heavy  residue  mixed  in  such  pro- 
portions as  to  give  the  density  desired. 

(3)  It  should  not  have  been  distilled  at  a  temperature  high  enough 
to  burn  it,  nor  at  a  temperature  so  high  that  flecks  of  carbonaceous 
matter  began  to  separate. 

*  J.  C.  Allen,  J.  Ind,  and  Eng.  Chem.,  3,  730  (1911). 


COAL  AND   FUEL  OIL  SPECIFICATIONS.         131 

(4)  It  should  not  flash  below  60°  C.  (140°  F.)  in  a  closed  Abel- 
Pensky  or  Pensky-Martens  tester. 

(5)  Its  specific  gravity  should  range  from  0.85  to  0.96  at  15°  C. 
(59°  F-);  the  oil  should  be  rejected  if  its  specific  gravity  is  above  0.97 
at  that  temperature. 

(6)  It  should  be  mobile,  free  from  solid  or  semi-solid  bodies,  and 
should  flow  readily,  at  ordinary  atmospheric  temperatures  and  under 
a  head  of  i  foot  of  oil,  through  a  4-inch  pipe  10  feet  in  length. 

(7)  It  should  not  congeal  nor  become  too  sluggish  to  flow  at  o°  C. 
(32°  F.). 

(8)  It  should  have  a  calorific  value  of  not  less  than  10,000  calories 
per  gram  *  (18,000  B.T.U.  per  pound),  10,250  calories  to  be  the  standard. 
A  bonus  is  to  be  paid  or  a  penalty  deducted  according  to  the  method 
stated  under  Section  21,  as  the  fuel  oil  delivered  is  above  or  below 
this  standard,  f 

(9)  It  should  be  rejected  if  it  contains  more  than  2  per  cent  water. 

(10)  It  should  be  rejected  if  it  contains  more  than  i  per  cent  sulphur, 
(n)  It  should  not  contain  more  than  a  trace  of  sand,  clay,  or  dirt. 

(12)  Each  bidder  must  submit  an  accurate  statement    regarding 
the  fuel  oil  he  proposes  to  furnish.     This  statement  should  show: 

(a)  The  commercial  name  of  the  oil. 

(b)  The  name  or  designation  of  the  field  from  which  the  oil  is  obtained. 

(c)  Whether  the  oil  is  a  crude  oil,  a  refinery  residue,  or  a  distillate. 

(d)  The  name  and  location  of  the  refinery ,[if  the  oil  has  been  refined 
at  all. 

(13)  The   fuel   oil  is  to  be  delivered  f.o.b.  cars  or  vessel,  according 
to  the  manner  of  shipment,  at  such  places,  at  such  times,  and  in  such 
quantities  as  may  be  required,  during  the  fiscal  year  ending 

(14)  Should  the  contractor,  for  any  reason,  fail  to  comply  with  a 
written  order  to  make  delivery,  the  Government  is  to  be  at  liberty  to 
buy  oil  in  the  open  market,  and  charge  against  the  contractor  any  excess 
of  price,  above  the  contract  price,  of  the  fuel  oil  so  purchased. 

*  Calories  X  i -8  =  B.T.U.  per  pound. 

t  It  is  important  that  the  standard  fixed  should  not  be  higher  than  can  be 
maintained  under  the  terms  of  the  contract.  In  the  absence  of  information 
as  to  the  heating  value  of  the  oil,  the  Bureau  of  Mines  will  analyze  samples 
taken  from  the  deliveries  to  establish  the  standard  heating  value,  expressed 
in  calories  or  B.T.U.  It  will  be  to  the  best  interests  of  the  contractor  to  specify 
a  fair  standard  for  the  fuel  oil  he  offers,  since  failure  to  maintain  that  standard 
will  cause  deduction  from  the  contract  price  and  possibly  the  cancellation 
of  the  contract,  while  deliveries  of  higher  quality  than  the  standard  will  result 
in  the  contractor  receiving  premiums. 


132  APPENDIX. 


SAMPLING. 

(15)  Deliveries  of  fuel  oil  will  be  sampled  by  a  representative  of  the 
Government.     Whenever  such  action  is  practicable,   the  oil  will  be 
sampled  as  it  is  being  delivered.     The  final  sample  will  be  made  from 
samples  taken  from  as  large  a  proportion  of  the  delivery  as  practicable, 
in  order  that  the  final  sample  may  truly  represent  the  delivery. 

(16)  The  final  sample  will  be  sealed  and  forwarded  to  the  Federal 
Bureau  of  Mines,  Pittsburgh,  Pa.,  for  analysis. 

(17)  If  the  contractor  so  desires,  permission  will  be  given  him,  or 
his  representative,  to  witness  the  sampling  of  the  delivery  and  the 
preparation  of  the  final  sample. 

(18)  The  final  sample  will  be  analyzed  and  tested  immediately  after 
its  receipt  in  Pittsburgh. 

CAUSES  FOR  REJECTION. 

(19)  A  contract  entered  into  under  the  terms  of  these  specifications 
shall  not  be  binding  if,  as  the  result  of  a  practical  service  test  of  reason- 
able duration,  the  fuel  oil  fails  to  give  satisfactory  results. 

(20)  It  is  understood  that  the  fuel  oil  delivered  during  the  terms  of 
the  contract  shall  be  of  the  quality  specified.    The  frequent  or  con- 
tinued failure  of  the  contractor  to  deliver  oil  of  the  specified  quality 
will  be  considered  sufficient  cause  for  the  cancellation  of  the  contract. 

PRICE  AND  PAYMENT. 

(21)  Payment  for  deliveries  will  be  made  on  the  basis  of  the  price 
named  in  the  proposal  for  the  fuel  oil  corrected  for  variations  in  heat- 
ing value,*  as  shown  by  analysis,  above  or  below  the  standard  fixed 
by  the  contractor.    This  correction  is  a  pro  rata  one  and  the  price  is 
to  be  determined  by  the  following  formulae: 

Delivered  calories  per  gram  (or  B.T.U.per  lb.)X contract  price 
Standard  calories  per  gram  (or  B.T.U.  per  Ib.) 

=  price  to  be  paid. 

*  The  value  of  an  oil  as  fuel  is  in  proportion  to  the  total  combustible  matter 
it  contains  as  shown  by  its  heating  value.  This  value  may  be  expressed  in 
small  calories  per  gram  of  B.T.U.  per  pound.  Sulphur,  moisture,  and  earthy 
matter  lower  the  heating  value  of  an  oil  and  decrease  the  furnace  capacity; 
they  also  may  have  a  deleterious  effect  on  boiler  and  furnace,  and  may  impair 
the  operation  of  burners. 


COAL   AND   FUEL  OIL  SPECIFICATIONS.          133 

Water  that  accumulates  in  the  receiving  tank  will  be  drawn  off  and 
measured  periodically.  Proper  deduction  will  be  made  by  subtracting 
the  weight  of  the  water  from  the  weight  of  the  oil  deliveries. 

DETERMINATION  OF  WEIGHT  FROM  VOLUME. 

The  specifications  given  on  the  preceding  pages  provide  for  the 
purchase  of  fuel  oil  by  weight.  As  such  oil  is  frequently  delivered  by 
volume,  it  is  important  to  note  the  temperature  of  a  delivery  and  to 
allow  for  the  expansion  due  to  this  temperature  when  computing  the 
weight  of  the  delivery  from  the  volume.  From  the  volume  of  the  oil 
at  the  temperature  of  delivery,  the  volume  at  standard  temperature 
(15°  C.)  should  be  computed  in  the  manner  given  below. 

The  coefficient  of  expansion  of  ordinary  fuel  oil  residues  of  asphaltic 
base  is  approximately  0.0006  per  i°  C. 

Hence  if  the  temperature  (.V0  C.)  of  the  delivery  is  above  15°  C., 
then  (N°  C.  — 15°  C.)  Xo.ooo6  =  correction. 

This  correction  is  to  be  added  to  the  specific  gravity  at  N°  C.  to 
give  the  standard  specific  gravity,  that  at  15°  C. 

If  the  temperature  (N°  C.)  of  the  oil  delivered  is  below  15°  C.,  the 
correction  ((15°  C.-N°  C.)Xo.ooo6)  is  to  be  subtracted  from  the 
specific  gravity  at  15°  C. 

Since  a  gallon  of  water  at  a  temperature  of  15°  C.  weighs  8.3316  Ibs., 
the  weight  in  pounds  of  a  gallon  of  oil  at  15°  C.  is  8.3316  times  the  specific 
gravity  of  the  oil  at  that  temperature. 

Similarly,  since  a  cubic  foot  of  water  at  15°  C.  weighs  62.3425  Ibs., 
the  weight  in  pounds  of  a  cubic  foot  of  oil  at  15°  C.  is  62.3425  times  its 
specific  gravity  at  that  temperature. 

REPORTING  ANALYSES  OF  FUEL  OIL. 

The  following  form  is  used  by  the  Bureau  of  Mines  in  reporting  the 
results  of  an  analysis  of  a  sample  of  fuel  oil : 

DEPARTMENT   OF  THE   INTERIOR. 

BUREAU  OF  MINES. 

WASHINGTON,  D.  C., 191 — . 

SIR: 

In  reference  to  the sample  of  fuel  petroleum  represent- 

(Quantity.) 

ing of  petroleum  delivered  at  a  temperature  of  ....  °  C.  by 

(Quantity.) 

the as  a product,  from  the 

(Company  delivering.)    (Crude,  residue,  or  distillate.)  (Lease.) 


I34  APPENDIX. 

,   , ,  to  the  , 

(Field  or  district.)         (County.)  (State.)  (Department  receiving.) 

at on ,  I    have    the    honor    to    report    as 

(City.)  (Date  of  delivery.) 

follows: 

Specific  gravity  at  15°  C 

(Baume  at  59°  F.) 

Calorie  per  gram 

(B.T.U.  per  pound) 

Water,  per  cent 

Sulphur,  per  cent 

Earthy  matter,  sand,  etc.,  per  cent 

Flash-point,  °  C.  (Abel-Pensky,  or  Pensky-Mar- 

tens,  closed  tester) 

Burning  point,  °  C.  (same  tester,  opened) 

Remarks : 


The  above  information  is  for  the  use  of  the  Government  and  the  dealer  or 
operator  furnishing  the  oil.  It  is  to  be  considered  confidential  until  it  is  pub- 
lished by  the  United  States  Government. 

Respectfully, 

Chief  Clerk. 
Certified: 

Petroleum  Chemist. 
SAMPLING  PETROLEUM  OR  FUEL  OIL. 

GENERAL  STATEMENT. 

The  accuracy  of  the  sampling  and,  in  turn,  the  value  of  the  analysis 
must  necessarily  depend  on  the  integrity,  alertness,  and  ability  of  the 
person  who  does  the  sampling.  No  matter  how  honest  the  sampler 
may  be,  if  he  lacks  alertness  and  sampling  ability,  he  may  easily  make 
errors  that  will  vitiate  all  subsequent  work  and  render  the  results  of 
tests  and  analyses  utterly  misleading.  A  sampler  must  be  always  on 
the  alert  for  sand,  water,  and  foreign  matter.  He  should  note  any 
circumstances  that  appear  suspicious,  and  should  submit  a  critical 
report  on  them,  together  with  samples  of  the  questioned  oil. 


COAL  AND  FUEL  OIL  SPECIFICATIONS.          135 
SAMPLING  WAGON  DELIVERIES. 

SAMPLING  WITH  A  DIPPER. 

Immediately  after  the  oil  begins  to  flow  from  the  wagon  to  the 
receiving  tank,  a  small  dipper  holding  any  definite  quantity,  say,  0.5 
liter  (about  i  pint),  is  filled  from  the  stream  of  oil.  Similar  samples 
are  taken  at  equal  intervals  of  time  from  the  beginning  to  the  end  of 
the  flow — a  dozen  or  more  dipperfuls  in  all.  These  samples  are  poured 
into  a  clean  drum  and  well  shaken.  If  the  oil  is  heavy,  the  dipperfuls 
of  oil  may  be  poured  into  a  clean  pail  and  thoroughly  stirred.  For  a 
•  complete  analysis  the  final  sample  should  contain  at  least  4  liters  (about 
i  gallon).  This  sample  should  be  poured  into  a  clean  can,  soldered 
tight  and  forwarded  to  the  laboratory. 

It  is  important  that  the  dipper  be  filled  with  oil  at  uniform  intervals 
of  time  and  that  the  dipper  be  always  filled  to  the  same  level.  The 
total  quantity  of  oil  taken  should  represent  a  definite  quantity  of  oil 
delivered  and  the  relation  of  the  sample  to  the  delivery  should  be 
always  be  stated,  for  instance:  "i  gallon  sample  representing  i  wagon- 
load  of  20  barrels." 

CONTINUOUS  SAMPLING. 

Instead  of  taking  samples  with  a  dipper,  it  may  be  more  convenient 
to  take  a  continuous  sample.  This  may  be  taken  by  allowing  the 
oil  to  flow  at  a  constant  and  uninterrupted  rate  from  a  £-inch  cock  on 
the  under  side  of  the  delivery  pipe  during  the  entire  time  of  discharge. 
The  continuous  sample  should  be  thoroughly  mixed  in  a  clean  drum 
or  pail,  and  at  least  4  liters  (about  i  gallon)  of  it  forwarded  for  analysis. 
A  careful  examination  should  be  made  for  water,  and  if  the  first  dipperf ul 
shows  water  this  dipperful  should  be  thrown  into  the  receiving  tank 
and  not  mixed  with  the  sample  for  analysis. 

MIXED  SAMPLES. 

If  the  oil  delivered  during  any  definite  period  of  time,  say  one  month, 
be  from  the  same  source  and  of  uniform  quality  (but  only  in  case  it  is 
of  uniform  quality),  it  may  suffice  to  pour  definite  proportional  quanti- 
ties of  the  dipper  and  the  continuous  samples  taken  during  this  period 
into  a  tinned  can  or  drum  having  a  tight  screw  cap  or  bung.  An  iron 
drum  should  not  be  used,  since  even  a  clean  iron  surface  will  absorb 
sulphur  by  long  contact  with  a  sulphur-containing  oil,  and  this  sulphur 
will  be  lost  to  the  analyst.  At  the  end  of  the  month  a  number  of  round, 


136  APPENDIX. 

clean  stones  should  be  put  into  the  drum  and  the  drum  should  be  rolled 
to  insure  intimate  mixing.  Then  4  liters  (about  i  gallon)  of  the  gross 
sample  should  be  taken  for  analysis.  The  drum  should  be  drained, 
rinsed  clean  with  gasoline,  dried,  and  made  ready  for  a  second  sampling. 
The  all-important  point  is  that  the  gross  sample,  whatever  the 
manner  of  sampling,  shall  be  made  up  of  equivalent  portions  of  oil 
taken  at  regular  intervals  of  time,  so  that  the  sample  finally  forwarded 
for  analysis  will  truly  represent  the  entire  shipment. 

SAMPLING  A  LARGE  TANK  OR  RESERVOIR. 

Water  or  earthy  matter  settles  on  standing.  Hence,  before  a  large 
stationary  tank  or  reservoir  is  sampled  the  character  of  the  contents 
at  the  bottom  should  be  ascertained  by  dredging  with  a  long-handled 
dipper,  and  the  content  of  the  dipper  should  be  examined  critically. 
If  a  considerable  quantity  of  sediment  is  brought  up,  it  should  be  cause 
for  rejecting  the  oil. 

The  sampling  of  a  large  stationary  tank  or  reservoir  of  oil,  par- 
ticularly if  the  oil  has  stood  so  long  that  it  has  begun  to  stratify,  or 
form  layers  of  different  density,  may  be  done  as  follows: 

The  sampler  should  procure  an  ordinary  iron  pipe,  or  preferably  a 
tinned  tube,  i  inch  in  diameter  and  long  enough  to  reach  from  above 
the  manhole,  where  he  can  grasp  it,  to  the  bottom  of  the  tank.  The 
lower  end  of  the  pipe  should  be  reamed  out  with  a  round  file.  A  conical 
plug  of  cork,  wood,  or  other  suitable  material  should  be  fitted  to  this 
end,  and  a  strong,  stiff  wire,  such  as  the  ordinary  telegraph  wire,  run 
through  this  plug  and  up  through  the  pipe  to  a  point  where  it  can  be 
grasped  firmly  by  the  sampler.  A  pull  on  the  wire  will  close  the 
bottom  of  the  pipe,  and  a  rap  against  the  bottom  of  the  tank  will  drive 
the  plug  home  and  make  an  oil-tight  seal  or  valve. 

To  operate  this  sampling  device,  the  sampler  should  remove  the 
plug,  allow  it  to  drop  some  three  inches  below  the  bottom  of  the  pipe, 
and  let  it  hang  there  by  the  wire  extending  above  the  pipe.  Then 
holding  the  pipe,  open  at  top  and  bottom,  in  a  vertical  position,  the 
sampler  should  allow  it  to  sink  slowly  through  the  oil  to  the  bottom 
of  the  tank.  He  should  do  this  slowly  and  with  care,  so  that  the  pipe 
will  penetrate  the  oil  without  agitating  it  and  will  thus  cut  a  repre- 
sentative core  of  oil  from  the  surface  to  the  bottom.  When  the  pipe 
touches  the  bottom,  the  sampler  should  draw  up  the  slack  of  the  wire 
and  pull  the  plug  into  place;  then  he  should  strike  the  plug  smartly 
against  the  bottom  of  the  tank,  thereby  driving  it  home  and  sealing 


COAL   AND  FUEL  OIL   SPECIFICATION'S.        137 

the  pipe.  He  can  then  withdraw  the  pipe  and  pour  the  oil  into  the 
sampling  can.  If  it  seems  desirable, Tie  should  "core  "  or  "sample" 
a  reservoir  at  regularly  spaced  points,  unite  these  samples,  mix  them 
thoroughly,  and  take  4  liters  (about  i  gallon)  of  the  gross  sample  for 
analysis. 

Instead  of  a  pipe  sampler,  a  bottle  holding  half  a  liter  (about  i  pint) 
may  be  used.  It  should  be  securely  fastened  to  a  long  pole  and  have 
a  loosely-fitted  stopper  tied  to  a  strong  cord.  The  bottle,  corked  and 
empty,  is  immersed  to  any  desired  point  within  the  mass  of  oil,  and  the 
stopper  is  pulled  out.  The  bottleful  of  oil  is  poured  into  a  suitable 
receiving  vessel,  and  the  bottle  thoroughly  drained  is  made  ready  for 
a  second  filling.  Bottlefuls  of  oil  taken  in  this  way  from  points  sym- 
metrically placed  throughout  the  mass  of  oil,  will,  if  properly  mixed, 
provide  an  excellent  gross  sample  from  which  to  take  the  4-liter  (i  gallon) 
sample  for  analysis. 

SAMPLING  A  SINGLE  DRUM. 

A  single  drum  may  be  sampled  with  a  glass  tube.  This  tube,  open 
at  both  ends,  should  be  grasped  at  the  top,  held  vertically,  inserted  in 
the  drum  without  agitating  the  oil,  and  allowed  to  cut  its  way  slowly 
to  the  bottom  of  the  drum.  The  upper  end  should  then  be  closed  with 
the  thumb  or  forefinger  of  the  hand  holding  it,  the  tube  withdrawn, 
and  the  oil  on  the  outside  wiped  off  with  the  fingers  of  the  other  hand. 
The  sample  in  the  tube  can  then  be  transferred  to  a  small  can,  and 
forwarded  for  analysis. 

FORWARDING  SAMPLES. 

The  sample  should  be  forwarded  in  a  glass  bottle  or  carboy  or  in  a 
tin  can,  preferably  in  the  latter,  because  less  liable  to  breakage.  If  a 
tin  can  is  used  the  cap  should  be  soldered  tight.  The  can  should  not 
be  filled  completely;  about  an  eighth  of  an  inch  of  space  should  be 
left  to  allow  for  possible  expansion  of  the  oil. 

The  can  should  be  sealed  as  soon  as  it  is  filled  to  avoid  loss  by  vola- 
tilization of  the  lighter  constituents  of  the  sample.  After  the  can  has 
been  filled  and  tightly  soldered,  it  should  be  wiped  clean  and  carefully 
examined  for  pinholes  or  small  leaks.  All  leaks  should  be  soldered 
before  the  can  is  packed  for  shipment. 

The  bottle  or  can  should  be  carefully  labeled.  The  following  form 
of  label,*  used  by  the  Bureau  of  Mines,  should  be  placed  on  samples 
shipped  to  the  bureau: 

*  These  labels  will  be  furnished  on  request. 


138  APPENDIX. 


DEPARTMENT  OF  THE  INTERIOR. 

BUREAU  OF  MINES. 

Information  to  Accompany  Each  Sample  of  Fuel  Petroleum  Submitted 
for  Analysis, 

Sample  number Sampled  by 

Oil  delivered  to 

(Department  receiving.) 

Place  of  delivery 

(City.)  (State.) 

Quantity  of  oil  delivered 

Date  of  delivery 

Temperature  of  oil  as  delivered  . . .  .  °  C 

Name  of  contractor 

Nature  of  oil 

(Crude,  residue,  or  distillate.) 

If  refined  to  any  degree,  state  name  and  location  of  refinery 


Source  of  oil 

(Lease.)  (Field  or  district.)          (County.)  (State.) 

Remarks.  . 


Date  of  forwarding  sample 

Forwarded  by via 

(Express  or  fast  freight.)  (Transportation  line.) 


Date  of  receipt  of  sample  by  Bureau  of  Mines 

Condition  of  sample  when  received  by  Bureau  of  Mines . 


The  label  should  be  carefully  written  with  a  hard  lead  pencil  on  a 
strong  mailing  tag,  and  this  tag  should  be  securely  tied  to  the  can. 
The  lead  pencil  should  be  pressed  firmly  against  the  tag  so  as  to  indent 
its  surface.  An  inscription  thus  written  is  legible  even  after  the  paper 
has  been  wet  with  oil.  Gummed  labels  should  not  be  used;  they  are 
easily  detached  if  slightly  moistened,  and  may  be  lost.  A  duplicate 
copy  of  the  record  on  the  label  should  be  mailed  to  the  engineer  in  charge, 
Bureau  of  Mines,  Pittsburgh,  Pa. 


COAL  AND   FUEL   OIL    SPECIFICATIONS.        139 


SAMPLING  GAS  FROM  A  WELL. 

Since  the  gas  associated  with  oil  is  an  ideal  fuel  and  illuminant,  and 
the  literature  dealing  with  the  composition  of  natural  gas  is  scanty, 
a  description  of  the  method  of  sampling  such  gas  for  analysis  is  here 
given. 

For  taking  a  sample  of  gas  under  pressure  from  an  oil  well  a  cloth 
funnel  should  be  made  by  folding  and  sewing  any  strong,  closely-woven 
cloth  into  the  form  of  a  cornucopia.  The  larger  end  of  this  funnel 
should  be  large  enough  to  encompass  the  gas  pipe  from  which  the 
sample  is  to  be  taken.  The  smaller  end,  or  apex,  of  the  funnel  should 
should  be  securely  tied  about  one  end  of  a  flexible  rubber  tube  i  or  2  feet 
long  and  one-fourth  to  one-half  inch  in  diameter.  If  there  is  a  gas  jet 
at  the  well,  one  end  of  the  rubber  tube  may  be  attached  directly  to  the 
jet. 

A  gas-sampling  bottle  should  be  procured,  if  practicable,  from  the 
Bureau  of  Mines,  Pittsburgh,  Pa.  If  such  a  bottle  is  not  at  hand,  a 
i-  or  2-liter  (i-  or  2-quart)  bottle  with  a  well-ground,  tight-fitting  glass 
stopper  may  be  used.  The  bottle  should  be  thoroughly  cleansed  and 
dried.  A  large  perfume  bottle  or  an  acid  bottle,  such  as  may  be  obtained 
from  a  drug  store,  will  usually  answer.  A  glass  stopper  is  essential, 
for  a  cork  or  rubber  stopper  may  leak  even  though  it  appears  to  be 
hermetically  sealed  with  wax;  moreover,  a  cork  or  rubber  stopper 
may  contaminate  the  gas. 

To  collect  a  sample,  the  funnel  should  be  tied  firmly  about  the  end 
of  the  gas  pipe.  The  funnel  and  the  rubber  tube  should  then  be  thor- 
oughly flushed  with  the  gas  to  rid  them  of  air.  The  free  end  of  the  tube 
should  go  to  the  bottom  of  the  sample  bottle.  The  bottle  should  be 
fastened  bottom  up  and  the  gas  allowed  to  blow  strongly  into  it  for  at 
least  a  quarter  of  an  hour  to  insure  complete  expulsion  of  air.  If  the 
gas  pressure  is  low,  the  gas  should  be  allowed  to  blow  longer,  or  until 
it  is  certain  that  all  air  has  been  expelled  from  the  bottle.  Meanwhile 
the  stopper  of  the  bottle  should  have  been  well  greased  with  vaseline. 

While  the  gas  is  still  blowing  through  the  tube  the  tube  should  be 
slowly  withdrawn.  The  stopper  should  be  put  in  just  as  soon  as  the 
tube  is  withdrawn  and  should  be  turned  firmly  into  place.  Then  the 
bottle  should  be  turned  up  and  a  spoonful  of  melted  paraffin  poured 
over  the  stopper.  The  stopper  should  be  secured  with  elastic  band. 

A  strong  tag  should  be  tied  to  the  bottle  by  a  stout  cord.  This  tag 
should  be  labeled  as  follows: 


140  APPENDIX. 

Gas  Sample. 


Sampled  by 

Date 

Well Lease 

Number. 

Section Township .'Range, 

District County State.  . 

Remarks 


The  bottle  should  be  packed  securely  in  a  box  and  forwarded  to  the 
Bureau  of  Mines,  Pittsburgh,  Pa.  A  duplicate  copy  of  the  label 
should  be  sent  to  the  same  address. 


INDEX. 


PAGE 

Acetylene,  calorific  power  of 115 

Acid,  hydrochloric,  reagent 51 

Air-pumps,  Bunsen's 8 

,  Richards' 8 

,  steam 9 

Alcohol,  denatured,  calorific  power  of 115 

,  ethyl,  calorific  power  of 115 

,  methyl,  calorific  power  of 115 

Anthracite  coal,  analysis  of 63 

Aqueous  vapor,  specific  heat 30 

,  table  of 113 

Aspirator 9 

,  Muencke's 56 

Benzoic  acid,  calorific  power 97 

Benzophenon,  boiling-point 26 

Berthier's  method  of  determining  calorific  power  of  coal 99 

Bituminous  coal,  analysis  of 62 

,  varieties ^. 61 

Blast-fumace  gas,  analysis  of 68 

Boiling-point  of  various  substances .• 26 

Brown  coal 61 

,  analysis  of 61 

,  calorific  power  of 116 

Bunte's  gas  apparatus 16 

method    for    determining  quantity  of  heat  passing  up 
chimney 32,  33 

Calculations 28 

Calorimeters  of  Barrus 81 

Fischer 81 

Hempel 82 

Emerson 82 

Thompson,  L 82 

Thomson,  W 81 

141 


142  INDEX. 

PAGE 

Cane  sugar,  calorific  power 97 

Carbon  dioxide,  determination  of 13,  18,  21,  40 

,  specific  heat 30 

Carbonic  oxide,  determination  of 14,  19,  22,  40 

,  loss  due  to  formation  of 34 

,  specific  heat 30 

Charcoal,  analysis  of 64 

,  preparation 63 

Coal,  air  required  for  combustion 63 

,  calorific  power 63 

,  formation  of 60 

,  method  of  analysis 7° 

specifications 119 

Coal-gas,  analysis  of 69 

,  calorific  power 69 

,  manufacture  of 69 

Coke,  analysis  of 64 

,  calorific  power  of 1 16 

,  determination  of 69 

,  preparation 64 

Coke-oven  gas,  calorific  power 70 

Coke-ovens 64 

Cooling  correction  in  calorimetry 90 

Course  in  gas  analysis 68 

Cuprous  chloride  acid,  reagent 51 

,  ammoniacal,  reagent 52 

Elliott's  gas  apparatus 20 

Emerson  bomb 82 

Formulas,  Bunte's,  for  calorific  power  of  coal 100 

,  Lunge's,  for  heat  passing  up  chimney 34 

,  Noyes',  for  calculation  of  heat  lost 34 

,  Ratio  of  air  used  to  that  theoretically  necessary 32 

Fuel,  determination  of  calorific  power 81, 102 

,  loss  due  to  unconsumed 34 

Fuel  oil,  specifications 13° 

Fuels,  method  of  analysis  of:  ash 78 

carbon 74 

coke  and  volatile  matter 73 

hydrogen 74 

moisture 73 


INDEX.  143 

PAGE 

Fuels,  method  of  analysis  of:  nitrogen 78 

oxygen 78 

sulphur 78 

Fuming  sulphuric  acid,  reagent 51 

Gas-balance  of  Custodis 24 

calorimeter,  Junkers' 102 

composimeter  of  Uehling 24 

Gas,  determination  of  calorific  power  by  calculation 107 

,  ignition  temperatures  of 114 

laboratory,  arrangement  of 55 

Gasolene,  calorific  power  of 115 

Generator  gas,  see  Producer-gas. 

Hempel's  gas  apparatus 36,  47 

Hydrocarbons,  determination  of 14,  23,  40 

Hydrogen,  determination  of 42,  46 

,  reagent 53 

Ignition  temperatures  of  gases 114 

" Illuminants,"  calorific  power  of iT5 

determination  of 41 

Illuminating-gas,  Boston,  analysis  of 108 

,  calorific  power  (calculated) no 

,  manufacture 70 

,  method  of  analysis  of 40 

Iron  tubes,  action  of  uncooled  gases  upon 2 

wire,  calorific  power 96 

Junkers'  gas  calorimeter 102 

Kerosene,  calorific  power  of 115 

Laboratory,  arrangement  of 55 

Lead,  quantity  reduced,  a  measure  of  the  calorific  power 99 

Lignite 61 

Melting-point  boxes 27 

Melting-point  of  various  substances 117 

Mercury,  reagent 53 

Methane,  determination  of 42,  46 

Moisture  in  coal,  determination  of 73 


144  INDEX. 

PAGE 

Naphthalene,  boiling-point 26 

,  calorific  power g6 

Natural  gas,  analysis  of 68 

,  calorific  power 70 

Nitrogen,  determination  of,  in  coal 78 

,  in  gases 14,  48 

,  specific  heat 30 

Orsat's  gas  apparatus n 

Otto-Hoffman  coke-ovens 64 

Oxygen,  determination  of,  in  air 40,  41 

,  in  coal 78 

,  in  gases 14,  19,  22,  43 

,  specific  heat 30 

Palladous  chloride,  reagent 54 

Peat,  analysis  of 60 

briquettes 59 

,  calorific  power 60 

,  formation 59 

,  moisture  in 59 

Petroleum,  crude,  analysis  of 68 

,  calorific  power 67 

,  formation  of 67 

Phosphorus,  reagent 54 

Potassium  hydrate,  reagent 54 

pyrogallate,  reagent 54 

"  Pounds  of  air  per  pound  of  coal " 28 

Producer-gas,  analysis  of 68 

,  calorific  power 69 

Pyrometer,  Le  Chatelier's  thermoelectric 26 

Quantity  of  heat  passing  up  chimney 29,  32 

Ratio  of  air  used  to  that  theoretically  necessary 32 

Sampling  apparatus 3,  6 

gases,  method  of a 

,  tubes  for 2 

solid  fuels,  method  of 69 

Scmet-Solvay  coke-ovens 64 


INDEX 


145 


PAGE 

Semi-bituminous  coal,  analysis  of 62 

Sodium  hydrate,  reagent 55 

pyrogallate,  reagent 55 

Specific  heat  of  various  gases 30 

Specifications  for  coal 119 

fuel  oil 130 

Spontaneous  combustion 66 

Storage  of  coal 66 

Sugar,  calorific  power 97 

Sulphur,  boiling-point 26 

Sulphuric  acid,  fuming,  reagent 51 

Table  of  calorific  power  of  gases 115 

liquids 115 

solids 116 

melting-points  of  metals  and  salts 117 

metric  and  English  systems 118 

quantity  of  air  necessary  to  burn  gases 114 

solubility  of  gases 117 

specific  gravity  of  gases 1 16 

tension  of  aqueous  vapor 113 

theoretical  quantity  of  air  supplied 118 

volumetric  specific  heats  of  gases 113 

weight  of  aqueous  vapor  in  air 113 

weights  of  gases 116 

Tanbark,  calorific  power  of 116 

Temperature,  measurement  of 25 

Thermometers 25 

,  testing  of 26 

Tubes  for  sampling .'  2 

Volatile  matter,  determination  of 70 

Water-gas,  analysis  of 69 

,  calorific  power 69 

Wheat  straw,  calorific  power 116 

Wood,  analysis  of 59 

,  calorific  power 59 

,  moisture  in 58,  59 


14  DAY  USE 

RETURN  TO  DESK  FROM  WHICH  BORROWED 

LOAN  DEPT. 

RENEWALS  ONLY-— TEL.  NO.  642-3405 
This  book  is  due  on  the  last  date  stamped  below,  or 

on  the  date  to  which  renewed. 
Renewed  books  are  subject  to  immediate  recall. 


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